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Alphabetical Index A B C D E F G H I J K L M N O P Q R S T U
V W X Y Z

A
Absorption of light
Accuracy
Acid-base definitions
Acid-base equilibria
Acid-base titrations
Activity and activity coefficients
Alpha plots
Analytical balance
Analytical chemistry (introduction)
Analytical standards
Anodic-stripping voltammetry
Atomic-absorption spectroscopy (AAS)
Atomic-emission gas chromatography detector (AED)
Atomic-emission spectroscopy (AES, OES)
Atomic energy levels
Atomic-fluorescence spectroscopy (AFS)
Atomic transitions (theory)
Auger-electron spectroscopy (AES)

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Absorption
Introduction
Matter can capture electromagnetic radiation and convert the energy of a photon to internal
energy. This process is called absorption. Energy is transferred from the radiation field to the
absorbing species. We describe the energy change of the absorber as a transition or an excitation
from a lower energy level to a higher energy level. Since the energy levels of matter are
quantized, only light of energy that can cause transitions from one level to another will be
absorbed.

The type of excitation depends on the wavelength of the light. Electrons are promoted to higher
orbitals by ultraviolet or visible light, vibrations are excited by infrared light, and rotations are
excited by microwaves.

Absorption spectroscopy is one way to study the energy levels of the atoms, molecules, and
solids. An absorption spectrum is the absorption of light as a function of wavelength. The
spectrum of an atom or molecule depends on its energy-level structure, making absorption
spectra useful for identifying compounds.

Measuring the concentration of an absorbing species in a sample is accomplished by applying the


Beer-Lambert Law.

http://www.files.chem.vt.edu/chem-ed/spec/absorption.html, updated 01/24/2012 Top of Page


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Definitions of Accuracy and Precision


Accuracy
The accuracy of a measurement is how close a result comes to the true value. Determining the
accuracy of a measurement usually requires calibration of the analytical method with a known
standard.

Precision
Precision is the reproducibility of multiple measurements. It is usually described by the standard
deviation, standard error, or confidence interval. A separate document defines these quantitative
measures of precision.

Illustration of accuracy and precision

Related topics:
 data handling

http://www.files.chem.vt.edu/chem-ed/data/acc-prec.html, updated 01/24/2012 Top of Page


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Definitions of Acids and Bases


Bronsted-Lowry Definition of Acids and Bases
The Bronsted-Lowry definitions for acids and bases:

Acids are species that donate a proton (H+).


and
Bases are species that accept a proton.

Acid example:
HNO3 (aq) + H2O NO3-(aq) + H3O+(aq)

In this example, HNO3 is an acid and H2O is acting as a base.


NO3- is called the conjugate base of the acid HNO3, and H3O+ is the conjugate acid of the base
H2O.

Base example:
NH3 (aq) + H2O NH4+(aq) + OH-(aq)

In this example, NH3 is a base and H2O is acting as an acid. NH4+ is the conjugate acid of the
base NH3, and OH- is the conjugate base of the acid H2O.

A compound that can act as either an acid or a base, such as the H2O in the above examples, is
called amphiprotic.

Lewis Acids and Bases


The Bronsted-Lowry definition of acids and bases does not encompass all chemical compounds
that exhibit acidic and basic properties. A more general definition is that of Lewis acids and
bases:

A Lewis acid is an electron-pair acceptor.


and
A Lewis base is an electron-pair donor.

These definitions are broader than the Bronsted-Lowry definition in that they include many
compounds that do not have protons, but exhibit acid/base behavior. The Lewis definition
encompasses the Bronsted-Lowry definition: In the reaction of H+ and OH-, H+ is a Lewis acid
because it accepts an electron pair from the OH-. Since the OH- donates an electron pair we call
it a Lewis base.

As an example not described by the Bronsted-Lowry definition, Al3+ in water is a Lewis acid. It
reacts with water to form an aqua complex: the Al3+ accepts the electron-pair from water
molecules. In this example the water acts as a Lewis base.
http://www.files.chem.vt.edu/chem-ed/titration/bronsted.html, updated 01/24/2012 Top of Page
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Equilibria of Acids and Bases


Introduction
We will use the Bronsted-Lowry definitions for acids and bases:

Acids are species that donate a proton (H+).


and
bases are species that accept a proton.

Water
For the example of water, H2O H+ + OH-, the equilibrium constant is:

[H+] [OH-]
Keq = ----------
[H2O]
The concentration of water in a water solution is constant and this expression simplifies to:
Kw = (55.56 M)*Keq = [H+] [OH-]
where Kw is called the dissociation constant of water and equals 1.00x10-14 at room temperature.
The concentrations of [H+] and [OH-] therefore equal 1.00x10-7 M.

Acids
An acid in water will dissociate, that is it donates it proton. We call acids that dissociate
completely strong acids and acids that dissociate only partially weak acids.

Strong acid example:


HNO3 (aq) + H2O NO3-(aq) + H3O+(aq)

Keq = a very large number


In this example, HNO3 is an acid and H2O is acting as a base.
NO3- is called the conjugate base of the acid HNO3, and H3O+ is the conjugate acid of the base
H2O.

Bases
A base in water can accept a proton from water to produce OH-. Strong bases are salts of
hydroxide that dissociate completely in water, so this statement is redundant. But weak bases do
not have to contain hydroxide themselves, but they produce basic solutions by reacting with
water.

Weak base example:


NH3 (aq) + H2O NH4+(aq) + OH-(aq)

K = 1.8x10-5

In this example, NH3 is a base and H2O is acting as an acid. NH4+ is the conjugate acid of the
base NH3, and OH- is the conjugate base of the acid H2O.

A compound that can act as either an acid or a base, such as the H2O in the above examples, is
called amphiprotic.

http://www.files.chem.vt.edu/chem-ed/equilibr/acid-base.html, updated 01/24/2012 Top of Page


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Acid-Base Titrations
Introduction
Recall that titration is the quantitative measurement of an analyte in solution by reacting it
completely with a standardized reagent. Acids and bases react until one of the reactants is
consumed completely. A solution of base of known concentration can therefore be used to titrate
an acid solution of unknown concentration. Likewise, an acid solution of known concentration
can be used to titrate a base solution of unknown concentration.

Strong Acid and Strong Base


The point at which all of the analyte is consumed by titrant is called the equivalence point. The
following figure shows the titration of a strong acid with 0.100 M NaOH. For titration of a strong
acid with a strong base, the equivalence point occurs at a pH of 7. To reach the equivalence point
in this example required 0.0350 mL of titrant, or 0.00350 moles of OH-. The titration shows that
there were 0.00350 moles of acid in the original solution.

We can identify three different regions in this titration experiment. Before the equivalence point
the pH is determined by the concentration of unneutralized strong acid. At the equivalence point
the pH, 7, is determined by the dissociation of water. After the equivalence point the pH is
determined by the concentration of excess strong base that we are adding.

Weak Acid Titration


The following plot shows the titration curves of 0.1 M solutions of a strong acid and a weak acid
(acetic acid).
First note the initial pH of these solutions (the initial pH of the 0.1 M acetic acid is 2.9). For the
strong acid, the dominant pH-determining species were described above. For the weak acid
titration, we can also identify three dominant equilibria as titrant is added. Before the
equivalence point the dominant species are acetic acid and acetate ion. The presence of these two
species form a buffer, and the pH could be calculated by the Henderson-Hasselbalch equation. At
the equivalence point, all of the acetic acid has been neutralized and only acetate ion remains in
solution. The pH is therefore determined by the base hydrolysis reaction of the acetate with
water. The pH is approximately 8.8 (not 7!). After the equivalence point, the situation is the same
as for a strong acid and the pH is determined by the concentration of excess strong base.

An alternate plot to find the equivalence point is the first derivative of the data as shown below.
The slope of the titration curve is steepest at the equivalence point, and the first derivative plot
shows a maximum.
Adding sufficient titrant to neutralize one-half of the weak acid results in a solution with equal
amounts of the weak acid and its conjugate base. At this halfway point in the titration, the pH
equals the pKa of the acid. Plotting pH versus log([base]/[acid]) produces a line with a y-
intercept equal to the pKa. This is a plot of the Henderson-Hasselbalch equation:

pH = pKa + log{V/(E-V)}

where E is the titrant volume at the endpoint and V is the variable for titrant added. This equation
is the same as the one in the Exp. 5, which uses Ve and Vb for E and V respectively. This plot is
only linear from about 20% to 80% of the endpoint volume. The Henderson-Hasselbalch
equation does not predict accurate results outside of this range due to the assumptions in the
equation. The plot shown below uses the pH data from 5.0 mL to 20.0 mL on the weak acid
titration curve from above.
Acid-Base Indicators
In an acid-base titration, addition of titrant near the equivalence point causes the solution pH to
change drastically. This pH change is detectable with indicators that change color as a function
of pH. Indicators are weak acids that change color when they gain or lose their acidic proton(s).
The table lists a few common indicators with the color of their acidic and basic forms and the pH
range over which the color change occurs. (The listed endpoint color assumes titration of an acid
with base, i.e., increasing pH.)

Indicator Color pH Range


acidic endpoint basic

bromocresol green yellow green blue 4.0-5.6


methyl red red yellow yellow 4.4-6.2
bromothymol blue yellow green blue 6.2-7.6
phenolpthalein colorless light pink red 8.0-10
We call the point at which the indicator changes color the end point. The end point might differ
slightly from the equivalence point, and the difference between the equivalence point and the end
point is called the titration error. The titration error will usually be negligible if a suitable
indicator is available for use.

http://www.files.chem.vt.edu/chem-ed/titration/acid-base-titration.html, updated Top of


01/24/2012 10:35:34 Page
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Activity
Introduction
In all of the equilibria that we've discussed so far, we've assumed that the equilibria occur in
ideal solutions. Solutions that have a total ion concentration greater than approximately 0.001 M
cannot really be treated as ideal solutions. When ion concentrations become high enough so that
ions interact, the interactions affect solution equilibria. Equilibria are affected not only when the
concentrations of the ions involved in an equilibrium become high, but also when the
concentrations of spectator ions become high. Spectator ions are not involved directly in
equilibria, but they affect the environment of the ions that are part of an equilibrium.

To use an analogy, let's say that you and a date plan to meet five other couples at a skating rink.
When you and your date skate onto the rink you see the other couples and you could say that the
formal concentration was six couples per rink. Everyone skates around in pairs most of the time,
but on average one couple is "dissociated" at any given time. (The topic of why couples
dissociate and recombine is best left for a physical chemistry class.) You could describe the
equilibrium concentrations as five undissociated couples and one dissociated couple per rink and
even determine an equilbrium constant for couple dissociation:

(1)(1)
Kc = ------ = 0.20
(5)
The c subscript is used to indicate couple dissociation.

Now, what happens if one hundred little kids skate onto the rink? The little kids are rather
hyperactive and won't skate as couples themselves or with the adult couples, but they do tend to
cluster around any individual adult skater. The rate at which couples dissociate is the same as
before (for the usual reasons), but as soon as they dissociate the individual skaters now get
surrounded by little kids. The little kids shield individual skaters from other individual skaters,
making it more difficult for two skaters to recombine to form a couple. Now you might look
around and see that there are four undissociated and two dissociated couples per rink, and that
the individual skaters tend to be surrounded by little kids.
(2)(2)
Kc' = ------ = 1
(4)
We put a ' on the equilibrium constant to specify new conditions.

The presence of little kids has drastically affected couple equilibrium! You can imagine that if
there were 500 little kids on the skating rink, the shielding between isolated adult skaters would
be even greater. Similarly, if there were only ten little kids scattered around the rink, they
probably wouldn't affect the equilibrium concentrations of the undissociated and dissociated
couples very much. We could call the situation when there were no or very few little kids on the
skating rink the dilute or ideal case.

In the above analogy, the undissociated and dissociated couples represented solutes in an
equilibrium and the little kids represented spectator ions. Note that for the little kids to affect the
equilibrium, there had to be an attraction between the little kids and the individual adult skaters.

Ions in solution have electrostatic interactions with other ions. Neutral solutes do not have such
interactions. When the concentrations of ions in a solution is greater than approximately 0.001
M, a shielding effect occurs around ions similar to the little kids around individual adults.
Cations tend to be surrounded by nearby anions and anions tend to be surrounded by nearby
cations. This shielding effect becomes significant at ion concentrations of 0.01 M and greater.
Doubly or triply charged ions "charge up" a solution more than singly charged ions, so we need a
standard way to talk about charge concentration. We describe the charge concentration of a
solution by the ionic strength, which is calculated from the following expression:

where
zi is the charge on an ion.
Ci is the formal concentration of each ion.
Note that the charge is squared so that positive and negative charges do not cancel. The factor of
1/2 is present because for every positive charge there is a negative charge.

Now, we could tabulate equilibrium constants for acid dissociation equilibria at different ionic
strengths, but that would be a lot of work and create huge tables. Ka values are usually tabulated
for the ideal case of zero ionic strength (and 25 oC). Appendix II of Rubinson & Rubinson
specifies if a Ka value was measured at other conditions.

We call the "effective concentration" of ions in solution activity and we relate it to the ideal
concentration by the activity coefficient, i:
These activity coefficients serve as correction factors so that equilibrium constants measured in
an ideal solution can be used to predict equilibria in non-ideal solutions.

Activity coefficients are unitless numbers that are calculated from the Debye-Hückel equation:

where
µ is the ionic strength of the solution.
zi is the charge on the ion.
i is the effective diameter of the hydrated ion in nanometers (nm), wich can be looked up in
tables (see below).
The constants in this equation are for aqueous solution at 25 oC.

Since the Debye-Hückel equation contains the charge and hydrated diameter of a specific ion,
each ion in a solution could have a different calculated activity coefficient. (Experimental
measurements give only an average activity coefficient for the ions that are present.) The ionic
strength is a description of the solution and the same value of µ is used for calculating the
activity coefficients of each ion in solution.

Example: What is the pH of 0.0200 M benzoic acid in water and in a solution of 0.10 M CaCl2?

Since benzoic acid is a weak acid, it will exist mostly as C6H5COOH in water, so the
concentration of ions will be very small. The ionic strength will be very close to zero and activity
coefficients will be one for ionic solutes.

[H+]2 + 6.28x10-5[H+] - 1.26x10-6 = 0

Solve using the quadratic equation:

[H+] = 1.09x10-3

pH = 2.96
Now let's repeat the calculation for benzoic acid in the CaCl2 solution. Since the ionic strength is
high we must use activities rather than concentrations.

C6H5COOH (aq) H+(aq) + C6H5COO-(aq)

We'll need the ionic strength, which we calculate using the charge and concentration of Ca2+ and
Cl-. As in the case of the water solution, the ion concentrations from the acid dissociation is
small and can be neglected.

With the ionic strength and the values (see below), we can calculate the activity coefficients
for H+ and C6H5COO-:
+
H = 0.9 nm
-
C6H5COO = 0.6 nm
[H+]2 + 1.09x10-4[H+] - 2.19x10-6 = 0

Solve using the quadratic equation:

[H+] = 1.43x10-3

pH = 2.84

We see that the shielding effect of the spectator ions increases the amount of acid dissociation by
approximately 30%. the H+ and benzoate ions are stabilized in solution by nearby spectator ions,
just like individual skaters were shielded by little kids from recombining into couples.

Effective hydrated diameters of ions in aqueous solution (25 oC).


cations anions i in nm
Rb+, Cs+, NH4+, Tl+, Ag+ 0.25
K+ Cl-, Br-, I-, NO3-, HCOO- 0.3
OH-, F-, HS-, ClO4-, MnO4- 0.35
Na+ HCO3-, H2PO4-, HSO3-, CH3COO- 0.4-0.45
Hg22+ HPO42-, SO42-, CrO42- 0.40
Pb2+ CO32-, SO32- 0.45
Sr2+, Ba2+, Cd2+, Hg2+ S2- 0.5
Li+, Ca2+, Cu2+, Zn2+
Phthalate2-, C6H5COO- 0.6
Sn2+, Mn2+, Fe2+, Ni2+, Co2+
Mg2+, Be2+ 0.8
H+, Al3+, Cr3+, Fe3+, La3+ 0.9
Th4+, Zr4+, Ce4+, Sn4+ 1.1

From J. Kielland, J. Am. Chem. Soc. 1937, 59, 1675.

To summarize: In dilute solutions ions are surrounded only by water molecules and the solution
behaves ideally, e.g., equilibrium constants give good predictions of equilibrium concentrations.
When ionic strength is larger than approximately 0.01 M, the shielding of ions affects equilibria
significantly. To use equilibrium constants that are tabulated for ideal solutions, we multiply
concentrations by correction factors called activity coefficients.

http://www.files.chem.vt.edu/chem-ed/equilibr/activity.html, updated 01/24/2012 Top of Page


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Alpha Fractions
Introduction
An fraction is the ratio of the equilibrium concentration of one specific form of a solute
divided by the total concentration of all forms of that solute in an equilibrium mixture. It is thus a
number between 0 and 1.

For the example of phosphoric acid, H3PO4:

H3PO4 (aq) H+(aq) + H2PO4-(aq) H+(aq) + HPO42-(aq) H+(aq) + PO43-(aq)

pKa1 = 2.15
pKa2 = 7.20
pKa3 = 12.38

Ctotal = [H3PO4] + [H2PO4-] + [HPO42-] + [PO43-]

0 = [H3PO4] / Ctotal

1 = [H2PO4-] / Ctotal

2 = [HPO42-] / Ctotal

3 = [PO43-] / Ctotal

Alpha fractions for a triprotic acid are calculated from the following equation:

[H+]3
0 = --------------------------------------
[H+]3 + Ka1[H+]2 + Ka1Ka2[H+] + Ka1Ka2Ka3

Ka1[H+]2
1 = --------------------------------------
[H+]3 + Ka1[H+]2 + Ka1Ka2[H+] + Ka1Ka2Ka3

Ka1Ka2[H+]
2 = --------------------------------------
[H+]3 + Ka1[H+]2 + Ka1Ka2[H+] + Ka1Ka2Ka3

Ka1Ka2Ka3
3 = --------------------------------------
[H+]3 + Ka1[H+]2 + Ka1Ka2[H+] + Ka1Ka2Ka3
Note that the denominators are the same in all of these equations. Plots of these four equations
are shown below for phosphoric acid. Figure 6.2 on page 186 of Rubinson & Rubinson shows
this plot on a log scale, which better shows the low concentrations.

See Figure 6.2 on page 186 of Rubinson & Rubinson to see this plot on a log scale.

Note that when the pH equals one of the pKa values, the acid to conjugate base ratio equals 1.

Why would we want to know the fraction of one particular species as a function of pH?

Example: adenosine diphosphate (ADP) adenosine triphosphate (ATP)

ADP(aq) + HPO42-(aq) + 2 H+(aq) ATP(aq) + H2O

This reaction has a positive G of 52.4 kJ/mol. Producing ATP is the body's way of storing
energy, e.g., doughnuts ATP. When your body needs energy for important activities like
thinking, ATP converts back to ADP to supply the energy.

Intracellular pH varies from 6.1 in muscle cells to approximately 7 in most other cells. Looking
at the phosphoric acid alpha plot, you can see that 2 varies from 0.07 to 0.4 over this range.

For the body to store energy it needs a reliable supply of HPO42-, which is one of many reasons
why buffer systems are so important in biology. Large changes in pH would convert HPO42- to
H2PO4- or PO43- and you would not be able to convert the chemical energy of doughnuts to a
usable form.
You might have noticed that Rubinson & Rubinson (Section 6.6, pg. 180) states that the
carbonate/bicarbonate equilibrium is the main determinant of blood pH, which is 7.4. The
carbonate system is the primary blood buffer, but look at the pKa values and the following alpha
plot to decide if a carbonate/bicarbonate equilibrium would create a buffer system at a pH of 7.4.

H2CO3 (aq) H+(aq) + HCO3-(aq) Ka = 4.45x10-7 pKa1 = 6.38


HCO3-(aq) + H2O CO32-(aq) + H3O+(aq) Ka2 = 4.7x10-11 pKa2 = 10.32

To achieve a pH of 7.4 requires bicarbonate ion and carbonic acid in a ratio of approximately 11.
Carbonate ion, CO32-, is present but in relatively low concentrations: 3 = 1.08x10-3. The HCO3-
to CO32- ratio might be important for other reasons, but it affects blood pH only indirectly.

As a side note, a blood pH of 7.4 is not in equilibrium with the atmospheric concentration of
CO2. The body maintains blood pH at 7.4 by the kidneys excreting excess acid and pumping
bicarbonate ion back into the blood.

http://www.files.chem.vt.edu/chem-ed/equilibr/alpha-plots.html, updated Top of


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Analytical Balance
Introduction
Analytical balances are accurate and precise instruments to measure weights. They require a
draft-free location on a solid bench that is free of vibrations. Modern balances have built-in
calibration weights to maintain accuracy. Older balances should be calibrated periodically with a
standard weight. A few weighing tips follow:

 Do not bump or place objects on the bench after zeroing the balance.
 Weigh powders on weighing paper or in weighing dishes. Handle objects with tongs,
gloves, or weighing paper to prevent fingerprints.
 Let hot objects cool before weighing.
 Weigh hygroscopic materials rapidly since they will absorb water during weighing.
 When making repetitive weighings always use the same procedure.

Picture of an analytical balance

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Introduction to Analytical Chemistry


Introduction
Analytical chemistry is the science of making quantitative measurements. In practice,
quantifying analytes in a complex sample becomes an exercise in problem solving. To be
effective and efficient, analyzing samples requires expertise in:

1. the chemistry that can occur in a sample


2. analysis and sample handling methods for a wide variety of problems (the tools-of-the-
trade)
3. proper data analysis and record keeping

To meet these needs, Analytical Chemistry courses usually emphasize equilibrium, spectroscopic
and electrochemical analysis, separations, and statistics.

Analytical chemistry requires a broad background knowledge of chemical and physical concepts.
These hypermedia documents contain links to the fundamental principles that underly the
different analytical methods. As you study the analytical chemistry topics, follow the hyperlinks
to the basic concepts with which you are not familiar. With a fundamental understanding of
analytical methods, a scientist faced with a difficult analytical problem can apply the most
appropriate technique(s). A fundamental understanding also makes it easier to identify when a
particular problem cannot be solved by traditional methods, and gives an analyst the knowledge
that is needed to develop creative approaches or new analytical methods.

Methods of Detecting Analytes


1. physical means
o mass
o color
o refractive index
o thermal conductivity
2. with electromagnetic radiation (Spectroscopy)
o absorption
o emission
o scattering
3. by an electric charge
o electrochemistry
o mass spectrometry

As you can see there are a limited number of ways to detect an analyte. However, in each of the
above general categories there are a large multitude of specific analytical techniques.

http://www.files.chem.vt.edu/chem-ed/crossref/ac-intro.html, updated 01/24/2012 Top of Page


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Analytical Standards
Introduction
Standards are materials containing a known concentration of an analyte. They provide a
reference to determine unknown concentrations or to calibrate analytical instruments.

The accuracy of an analytical measurement is how close a result comes to the true value.
Determining the accuracy of a measurement usually requires calibration of the analytical method
with a known standard. This is often done with standards of several concentrations to make a
calibration or working curve.

Primary Standards
A primary standard is a reagent that is extremely pure, stable, has no waters of hydration, and has
a high molecular weight.

Some primary standards for titration of acids:

 sodium carbonate: Na2CO3, mol wt. = 105.99 g/mol


 tris-(hydroxymethyl)aminomethane (TRIS or THAM): (CH2OH)3CNH2, mol wt. = 121.14 g/mol

Some primary standards for titration of bases:

 potassium hydrogen phthalate (KHP): KHC8H4O4, mol wt. = 204.23 g/mol


 potassium hydrogen iodate: KH(IO3)2, mol wt. = 389.92 g/mol

Some primary standards for redox titrations:

 potassium dichromate: K2Cr2O7, mol wt. = 294.19 g/mol

Secondary Standards
A secondary standard is a standard that is prepared in the laboratory for a specific analysis. It is
usually standardized against a primary standard.

NIST Standard Reference Materials


The National Institute of Standards and Technology (NIST) provide a wide variety of standard reference
materials (SRMs) for validating and calibrating analytical methods. Some examples of SRMs:

for chemical composition

 elements in iron, steels, and other metal alloys


 sulfur in fossil fuels
 polychlorinated biphenyls (PCBs) in oils
 elements in foods and beverages (e.g. milk powder, wheat flour)

for physical properties

 strength and melt fow of polyethylene pipe


 radioactivity
 electrical resistivity of Si

for engineering materials

 particle sizes
 magnetic computer storage media
 surface flammability

For more info see the NIST SRM website.

http://www.files.chem.vt.edu/chem-ed/data/standard.html, updated 01/24/2012 Top of Page


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Anodic Stripping Voltammetry


Introduction
Anodic stripping voltammetry is an electrolytic method in which a mercury electrode is held at a
negative potential to reduce metal ions in solution and form an amalgam with the electrode. The
solution is stirred to carry as much of the analyte metal(s) to the electrode as possible for
concentration into the amalgam. After reducing and accumulating the analyte for some period of
time, the potential on the electrode is increased to reoxidize the analyte and generate a current
signal. The ramped potential usually uses a step function, such as in normal-pulse polarography
(NPP) or differential-pulse polarography (DPP).

The concentration of the analyte in the Hg electrode, CHg, is given by:

il td
CHg = -------
n F VHg
where il is the limiting current during reduction of the metal, td is the duration of accumulation, n
is the number of moles of electrons transferred in the half reaction, F is the Faraday constant
(96,487 coulombs/mole of e-), and VHg is the volume of the electrode. The expression for current
produced by anodic stripping depends on the particular type of Hg electrode, but is directly
proportional to the concentration of analyte concentrated into the electrode. The main advantage
of stripping analysis is the preconcentration of the analyte into the electrode before making the
actual current measurement. Anodic stripping can achieve detection of concentrations as low as
10-10 M.

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Atomic-Absorption Spectroscopy (AA)


Introduction
Atomic-absorption (AA) spectroscopy uses the absorption of light to measure the concentration
of gas-phase atoms. Since samples are usually liquids or solids, the analyte atoms or ions must be
vaporized in a flame or graphite furnace. The atoms absorb ultraviolet or visible light and make
transitions to higher electronic energy levels. The analyte concentration is determined from the
amount of absorption. Applying the Beer-Lambert law directly in AA spectroscopy is difficult
due to variations in the atomization efficiency from the sample matrix, and nonuniformity of
concentration and path length of analyte atoms (in graphite furnace AA). Concentration
measurements are usually determined from a working curve after calibrating the instrument with
standards of known concentration.
Schematic of an atomic-absorption experiment

Instrumentation
Light source

The light source is usually a hollow-cathode lamp of the element that is being measured. Lasers
are also used in research instruments. Since lasers are intense enough to excite atoms to higher
energy levels, they allow AA and atomic fluorescence measurements in a single instrument. The
disadvantage of these narrow-band light sources is that only one element is measurable at a time.

Atomizer

AA spectroscopy requires that the analyte atoms be in the gas phase. Ions or atoms in a sample
must undergo desolvation and vaporization in a high-temperature source such as a flame or
graphite furnace. Flame AA can only analyze solutions, while graphite furnace AA can accept
solutions, slurries, or solid samples.

Flame AA uses a slot type burner to increase the path length, and therefore to increase the total
absorbance (see Beer-Lambert law). Sample solutions are usually aspirated with the gas flow
into a nebulizing/mixing chamber to form small droplets before entering the flame.

The graphite furnace has several advantages over a flame. It is a much more efficient atomizer
than a flame and it can directly accept very small absolute quantities of sample. It also provides a
reducing environment for easily oxidized elements. Samples are placed directly in the graphite
furnace and the furnace is electrically heated in several steps to dry the sample, ash organic
matter, and vaporize the analyte atoms.

Light separation and detection

AA spectrometers use monochromators and detectors for uv and visible light. The main purpose
of the monochromator is to isolate the absorption line from background light due to
interferences. Simple dedicated AA instruments often replace the monochromator with a
bandpass interference filter. Photomultiplier tubes are the most common detectors for AA
spectroscopy.
Picture of a flame atomic-absorption spectrometer

JavaScript tour of a Flame AA Spectrometer.

Picture of a graphite-furnace atomic-absorption spectrometer

Close-up of the graphite furnace | View of the control box

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Atomic-Emission Detector (AED)


Introduction
As capillary column based gas chromatography takes its place as the major, highest resolution
separation technique available for volatile, thermally stable compounds, the requirements for the
sensitive and selective detection of these compounds increases. Since more and more complex
mixtures can be successfully separated, subsequent chromatograms (output of a chromatographic
separation) are increasingly more complex. Therefore, the need to differentiate between the
sample components using the GC detector as a means of compounds discriminating is more and
more common. In addition, each detector has its own characteristics (selectivity, sensitivity,
linear range, stability, cost, etc.) that helps in a decision about which detector to use.

One of the newest additions to the gas chromatographer's arsenal is the atomic emission detector
(AED). This detector, while quite expensive compared to other commercially available GC
detectors, is an extremely powerful alternative. FOR INSTANCE, Instead of measuring simple
gas phase (carbon containing) ions created in a flame as with the flame ionization detector, or the
change in background current because of electronegative element capture of thermal electrons as
with the electron capture detector, the AED has a much wider applicability because it is based on
the detection of atomic emissions.

The strength of the AED lies in the detector's ability to simultaneously determine the atomic
emissions of many of the elements in analytes that elute from a GC capillary column (called
eluants or solutes in some books). As eluants come off the capillary column they are fed into a
microwave powered plasma (or discharge) cavity where the compounds are destroyed and their
atoms are excited by the energy of the plasma. The light that is emitted by the excited particles is
separated into individual lines via a photodiode array. The associated computer then sorts out the
individual emission lines and can produce chromatograms made up of peaks from eluants that
contain only a specific element.

Instrumentation
The components of the AED include 1) an interface for the incoming capillary GC column to the
microwave induced plasma chamber, 2) the microwave chamber itself, 3) a cooling system for
that chamber, 4) a diffraction grating and associated optics to focus then disperse the spectral
atomic lines, and 5) a position adjustable photodiode array interfaced to a computer. The
microwave cavity cooling is required because much of the energy focused into the cavity is
converted to heat.
Schematic of a gas chromatographic atomic emission detector

These notes were written by Dr. Thomas G. Chasteen at Sam Houston State University,
Huntsville, Texas.
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Atomic Emission Spectroscopy (AES, OES)


Introduction
Atomic emission spectroscopy (AES or OES [optical emission spectroscopy]) uses quantitative
measurement of the optical emission from excited atoms to determine analyte concentration.
Analyte atoms in solution are aspirated into the excitation region where they are desolvated,
vaporized, and atomized by a flame, discharge, or plasma. These high-temperature atomization
sources provide sufficient energy to promote the atoms into high energy levels. The atoms decay
back to lower levels by emitting light. Since the transitions are between distinct atomic energy
levels, the emission lines in the spectra are narrow. The spectra of samples containing many
elements can be very congested, and spectral separation of nearby atomic transitions requires a
high-resolution spectrometer. Since all atoms in a sample are excited simultaneously, they can be
detected simultaneously using a polychromator with multiple detectors. This ability to
simultaneously measure multiple elements is a major advantage of AES compared to atomic-
absorption (AA) spectroscopy.

Schematic of an AES experiment

Instrumentation
As in AA spectroscopy, the sample must be converted to free atoms, usually in a high-
temperature excitation source. Liquid samples are nebulized and carried into the excitation
source by a flowing gas. Solid samples can be introduced into the source by a slurry or by laser
ablation of the solid sample in a gas stream. Solids can also be directly vaporized and excited by
a spark between electrodes or by a laser pulse. The excitation source must desolvate, atomize,
and excite the analyte atoms. A variety of excitation sources are described in separate
documents:

 Direct-current plasma (DCP)


 Flame
 Inductively-coupled plasma (ICP)
 Laser-induced breakdown (LIBS)
 Laser-induced plasma
 Microwave-induced plasma (MIP)
 Spark or arc

Since the atomic emission lines are very narrow, a high-resolution polychromator is needed to
selectively monitor each emission line.
Picture of an inductively-coupled plasma atomic emission spectrometer

JavaScript tour of an

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Atomic Energy Levels


Introduction
The energy levels of atoms are quantized and have definite, discrete energies. The energies are
measured relative to the energy required to remove an electron, which is called the ionization
potential of the atom. The figure shows the energy levels for the H atom. Transitions between
energy levels that involve the absorption or emission of light is the field of spectroscopy.
H atom energy levels

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Atomic-Fluorescence Spectroscopy (AFS)


Introduction
Atomic fluorescence is the optical emission from gas-phase atoms that have been excited to
higher energy levels by absorption of electromagnetic radiation. The main advantage of
fluorescence detection compared to absorption measurements is the greater sensitivity achievable
because the fluorescence signal has a very low background. The resonant excitation provides
selective excitation of the analyte to avoid interferences. AFS is useful to study the electronic
structure of atoms and to make quantitative measurements. Analytical applications include
flames and plasmas diagnostics, and enhanced sensitivity in atomic analysis. Because of the
differences in the nature of the energy-level structure between atoms and molecules, discussion
of laser-induced fluorescence (LIF) from molecules is found in a separate document.
Instrumentation
Analysis of solutions or solids requires that the analyte atoms be desolvated, vaporized, and
atomized at a relatively low temperature in a heat pipe, flame, or graphite furnace. A hollow-
cathode lamp or laser provides the resonant excitation to promote the atoms to higher energy
levels. The atomic fluorescence is dispersed and detected by monochromators and
photomultiplier tubes, similar to atomic-emission spectroscopy instrumentation.

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Atomic Transitions - Theory


Introduction
The probability that an atomic spectroscopic transition will occur is called the transition
probability or transition strength. This probability will determine the extent to which an atom
will absorb light at a resonance frequency, and the intensity of the emission lines from an atomic
excited state. The spectral width of a spectroscopic transition depends on the widths of the initial
and final states. The width of the ground state is essentially a delta function and the width of an
excited state depends on its lifetime.

Specific Documents
 Transition strengths
 Excited-state lifetime and the natural linewidth
 Transition lineshapes and broadening

Related Topics
 Atomic absorption spectroscopy
 Atomic emission spectroscopy
 Atomic fluorescence spectroscopy
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Auger Electron Spectroscopy (AES)


Introduction
Auger (pronounced ~o-jay) electron spectroscopy is an electron spectroscopic method that uses a
beam of electrons to knock electrons out of inner-shell orbitals. Auger electrons are ejected to
conserve energy when electrons in higher shells fill the vacancy in the inner shell. These Auger
electrons have energies characteristic of the emitting atom due to the characteristic energy-level
structure of that element.

Instrumentation
Picture of an Auger electron spectrometer

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Beer-Lambert Law
Introduction
The Beer-Lambert law (also called the Beer-Lambert-Bouguer law or simply Beer's law) is the
linear relationship between absorbance and concentration of an absorber of electromagnetic
radiation. The general Beer-Lambert law is usually written as:

where A is the measured absorbance, a is a wavelength-dependent absorptivity coefficient, b is


the path length, and c is the analyte concentration. When working in concentration units of
molarity, the Beer-Lambert law is written as:

where is the wavelength-dependent molar absorptivity coefficient with units of M-1 cm-1.
The subscript is often dropped with the understanding that a value for is for a specific
wavelength. If multiple species that absorb light at a given wavelength are present in a sample,
the total absorbance at that wavelength is the sum due to all absorbers:

where the subscripts refer to the molar absorptivity and concentration of the different absorbing
species that are present.

Theory
Experimental measurements are usually made in terms of transmittance (T), which is defined as:

where P is the power of light after it passes through the sample and Po is the initial light power.
The relation between A and T is:
The figure shows the case of absorption of light through an optical filter and includes other
processes that decreases the transmittance such as surface reflectance and scattering.

In analytical applications we often want to measure the Absorption of light by a sample


concentration of an analyte independent of the effects
of reflection, solvent absorption, or other interferences.
The figure to the right shows the two transmittance
measurements that are necessary to use absorption to
determine the concentration of an analyte in solution.
The top diagram is for solvent only and the bottom is
for an absorbing sample in the same solvent. In this
example, Ps is the source light power that is incident on
a sample, P is the measured light power after passing
through the analyte, solvent, and sample holder, and Po
is the measured light power after passing through only
the solvent and sample holder. The measured
transmittance in this case is attributed to only the
analyte.

Depending on the type of instrument, the reference


measurement (top diagram) might be made
simultaneously with the sample measurement (bottom
diagram) or a reference measurement might be saved
on computer to generate the full spectrum.
Modern absorption instruments can usually display the data as either transmittance, %-
transmittance, or absorbance. An unknown concentration of an analyte can be determined by
measuring the amount of light that a sample absorbs and applying Beer's law. If the absorptivity
coefficient is not known, the unknown concentration can be determined using a working curve of
absorbance versus concentration derived from standards.

Derivation of the Beer-Lambert law


The Beer-Lambert law can be derived from an approximation for the absorption coefficient for a
molecule by approximating the molecule by an opaque disk whose cross-sectional area, ,
represents the effective area seen by a photon of frequency w. If the frequency of the light is far
from resonance, the area is approximately 0, and if w is close to resonance the area is a
maximum. Taking an infinitesimal slab, dz, of sample:
Io is the intensity entering the sample at z=0, Iz is the intensity entering the infinitesimal slab at z,
dI is the intensity absorbed in the slab, and I is the intensity of light leaving the sample. Then, the
total opaque area on the slab due to the absorbers is * N * A * dz. Then, the fraction of
photons absorbed will be * N * A * dz / A so,

Integrating this equation from z = 0 to z = b gives:

or

Since N (molecules/cm3) * (1 mole / 6.023x1023 molecules) * 1000 cm3 / liter = c (moles/liter)


and 2.303 * log(x) = ln(x), then

or
where = * (6.023x1020 / 2.303) = * 2.61x1020

Typical cross-sections and molar absorptivities are:

(cm2) (M-1 cm-1)


absorption - atoms 10-12 3x108
absorption - molecules 10-16 3x104
absorption - infrared 10-19 3x10
Raman scattering 10-29 3x10-9

Limitations of the Beer-Lambert law


The linearity of the Beer-Lambert law is limited by chemical and instrumental factors. Causes of
nonlinearity include:

 deviations in absorptivity coefficients at high concentrations (>0.01M) due to


electrostatic interactions between molecules in close proximity
 scattering of light due to particulates in the sample
 fluoresecence or phosphorescence of the sample
 changes in refractive index at high analyte concentration
 shifts in chemical equilibria as a function of concentration
 non-monochromatic radiation, deviations can be minimized by using a relatively flat part
of the absorption spectrum such as the maximum of an absorption band
 stray light

Related Topics
 Introduction to spectroscopy

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Bipolar Transistors
Introduction
Circuit symbol:

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Lamps
Introduction
Lamps convert electrical energy into radiation. Different designs and materials are needed to
produce light in different parts of the electromagnetic spectrum. The following sections describe
several different types of lamps that are useful in spectroscopy.

Blackbody Sources
A hot material, such as an electrically-heated filament in a light bulb, emits a continuum
spectrum of light. The spectrum is approximated by Planck's radiation law for blackbody
radiators:

B = {2h 3/c2}{1/exp(h /kT)-1}


where h is Planck's constant, is frequency, c is the speed of light, k is the Boltzmann constant,
and T is temperature in K.

The most common incandescent lamps and their wavelength ranges are:
tungsten filament lamps : 350 nm - 2.5 µm
glowbar : 1 - 40 µm
Nernst glower : 400 nm - 20 µm
Tungsten lamps are used in visible and near-infrared (NIR) absorption spectroscopy and the
glowbar and Nernst glower are used for infrared spectroscopy.

Discharge Lamps
Discharge lamps, such as neon signs, pass an electric current through a rare gas or metal vapor to
produce light. The electrons collide with gas atoms, exciting them to higher energy levels which
then decay to lower levels by emitting light. Low-pressure lamps have sharp line emission
characteristic of the atoms in the lamp, and high-pressure lamps have broadened lines
superimposed on a continuum.

Common discharge lamps and their wavelength ranges are:


hydrogen or deuterium : 160 - 360 nm
mercury : 253.7 nm, and weaker lines in the near-uv and visible
Ne, Ar, Kr, Xe discharge lamps : many sharp lines throughout the near-uv to near-IR
xenon arc : 300 - 1300 nm

Deuterium lamps are the uv source in UV-vis absorption spectrophotometers. The sharp lines of
the mercury and rare gas discharge lamps are useful for wavelength calibration of optical
instrumentation. Mercury and xenon arc lamps are used to excite fluorescence.

Hollow-cathode Lamps
Hollow-cathode lamps are a type of discharge lamp that produce narrow emission from atomic
species. They get their name from the cup-shaped cathode, which is made from the element of
interest. The electric discharge ionizes rare gas atoms, which are accelerated into the cathode and
sputter metal atoms into the gas phase. Collisions with gas atoms or electrons excite the metal
atoms to higher energy levels, which decay to lower levels by emitting light.

Schematic of a hollow-cathode lamp

Hollow-cathode lamps have become the most common light source for atomic absorption (AA)
spectroscopy. They are also sometimes used as an excitation source for atomic-fluorescence
spectroscopy (AFS).
Related Topics
 Optics
 Optical Materials

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Born-Oppenheimer Approximation
The Born-Oppenheimer Approximation
Since nuclear motion is much slower than electron motion the electronic wavefunction, or
energies, can be calculated assuming a fixed position of the nuclei and nuclear motion can be
considered assuming and average distribution of electron density.

This approximation allows us to:

1. Construct energy level diagrams like:

2. Total energy of a molecular state is the sum of:


3. Total wavefunction is the product of wavefunctions for the electrons and nuclei with
vibrational and rotational parts.

4. Nuclei remain fixed during much faster electronic transition - transitions are vertical.

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Definitions of Acids and Bases


Bronsted-Lowry Definition of Acids and Bases
The Bronsted-Lowry definitions for acids and bases:
Acids are species that donate a proton (H+).
and
Bases are species that accept a proton.

Acid example:
HNO3 (aq) + H2O NO3-(aq) + H3O+(aq)

In this example, HNO3 is an acid and H2O is acting as a base.


NO3- is called the conjugate base of the acid HNO3, and H3O+ is the conjugate acid of the base
H2O.

Base example:
NH3 (aq) + H2O NH4+(aq) + OH-(aq)

In this example, NH3 is a base and H2O is acting as an acid. NH4+ is the conjugate acid of the
base NH3, and OH- is the conjugate base of the acid H2O.

A compound that can act as either an acid or a base, such as the H2O in the above examples, is
called amphiprotic.

Lewis Acids and Bases


The Bronsted-Lowry definition of acids and bases does not encompass all chemical compounds
that exhibit acidic and basic properties. A more general definition is that of Lewis acids and
bases:

A Lewis acid is an electron-pair acceptor.


and
A Lewis base is an electron-pair donor.

These definitions are broader than the Bronsted-Lowry definition in that they include many
compounds that do not have protons, but exhibit acid/base behavior. The Lewis definition
encompasses the Bronsted-Lowry definition: In the reaction of H+ and OH-, H+ is a Lewis acid
because it accepts an electron pair from the OH-. Since the OH- donates an electron pair we call
it a Lewis base.

As an example not described by the Bronsted-Lowry definition, Al3+ in water is a Lewis acid. It
reacts with water to form an aqua complex: the Al3+ accepts the electron-pair from water
molecules. In this example the water acts as a Lewis base.

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Buffers (Acid-Base)
Introduction
A buffer is a solution that can maintain a nearly constant pH if it is diluted, or if strong acids or
bases are added. A buffer solution consists of a mixture of a weak acid and its conjugate base (or
a weak base and its conjugate acid).

Example: Consider a solution containing both acetic acid, CH3COOH, and acetate ions,
CH3COO-.

Any strong base that is added to the solution is neutralized by acetic acid:
CH3COOH (aq) + OH-(aq) CH3COO-(aq) + H2O (aq)

Any strong acid that is added to the solution is neutralized by acetate:


CH3COO-(aq) + H+(aq) CH3COOH (aq)

The amount of strong acid or base that a buffer can neutralize is called the buffer capacity.

Since the buffer concentration is usually high, the [H+] concentration can be calculated
from the equilibrium expression assuming that the concentrations of the conjugate acid-
base pair do not change appreciably.

Example: What is the pH of a buffer solution containing 0.100 moles of both CH3COOH and
CH3COO- in 0.100 L of water?

The equilibrium is:


CH3COOH(aq) CH3COO-(aq) + H+(aq) Ka = 1.8x10-5 (at 25 oC)

CH3COOH CH3COO- H+
[ ]o 1.00 M 1.00 M --
[ ] ~0 ~0 x
[ ]eq 1.00 M 1.00 M x

What is Q for these initial conditions? In which direction will the reaction shift to reach
equilibrium?

[H+][CH3COO-]
Ka = -------------
[CH3COOH]
1.8x10-5 = [H+] (1.00 M) / (1.00 M)
[H+] = 1.8x10-5
pH = -log(1.8x10-5) = 4.74

Notice that when the concentrations of the weak acid and conjugate base are equal, the pH of the
buffer solution equals pKa.

What happens if we add some strong acid to this buffer?

Example: What is the pH of the resulting solution when 10.0 mL of 1.00 M HCl is added to the
above buffer?

CH3COOH CH3COO- H+
(1.00 M)(0.100 L)/0.110 L (1.00 M)(0.100 L)/0.110 L (1.00 M)(0.010 L)/0.110 L
[ ]o
= 0.909 M = 0.909 M = 0.0909 M
[ ] +0.0909 M -0.0909 M ~ -0.0909 M
(0.909+0.0909) M (0.909-0.0909) M
[ ]eq x
= 1.00 M = 0.818 M
[H+][CH3COO-]
Ka = -------------
[CH3COOH]
1.8x10-5 = [H+] (0.818 M) / (1.00 M)
[H+] = 2.20x10-5
pH = -log(2.20x10-5) = 4.66

This problem can also be done using the number of moles of the acids and bases:

CH3COOH CH3COO- H+
moleso 0.100 mol 0.100 mol (1.00 M)(0.010 L) = 0.010 mol
(moles) +0.010 -0.010 ~ -0.010
0.100+0.010 0.100-0.010
moleseq x
=0.110 =0.090
[H+][CH3COO-]
Ka = -------------
[CH3COOH]
1.8x10-5 = [H+] (0.090) / (0.110)
[H+] = 2.20x10-5
pH = -log(2.20x10-5) = 4.66

In these problems how did we initially produce the 0.1 M CH3COOH and CH3COO-? In general
how can we make a buffer?
1. Mix a weak acid and a salt of its conjugate base in solution.
2. Mix a weak acid and enough strong base to neutralize some of the weak acid.
3. Mix a weak base and enough strong acid to neutralize some of the weak base.

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Calibration
Introduction
Making measurements with any analytical method or instrument requires calibration to ensure
the accuracy of the measurement. There are two common calibration procedures: using a
working curve, and the standard-addition method. Both of these methods require one or more
standards of known composition to calibrate the measurement.

Instrumental methods are usually calibrated with standards that are prepared (or purchased) using
a non-instrumental analysis. There are two direct analytical methods: gravimetry and
coulometry. Titration is similar but requires preparation of a primary standard.

The chief advantage of the working curve method is that it is rapid in that a single set of
standards can be used for the measurement of multiple samples. The standard-addition method
requires multiple measurements for each sample, but can reduce inaccuracies due to
interferences and matrix effects.

Related topics:
 data handling

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Capacitors
Introduction
Capacitors consist of a dielectric material separating two parallel plates. They are used to hold
charge or to transmit an ac signal and block a dc signal.

Circuit symbol:

Capacitance
Symbol: C, unit: farad (F)

Capacitance is the amount of charge a capacitor can hold per volt.

Q = CV, I = C(dV/dt)

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Capillary Electrophoresis (CE)


Introduction
Performing electrophoresis in small-diameter capillaries allows the use of very high electric
fields because the small capillaries efficientlydissipate the heat that is produced. Increasing the
electric fields produces very efficient separations and reduces separation times.

Instrumentation
Capillaries are typically of 50 � m inner diameter and 0.5 to 1 m in length. The applied potential
is 20 to 30 kV. Due to electroosmotic flow, all sample components migrate towards the negative
electrode. A small volume of sample (10 nL) is injected at the positive end of the capillary and
the separated components are detected near the negative end of the capillary. CE detection is
similar to detectors in HPLC, and include absorbance, fluorescence, electrochemical, and mass
spectrometry.

The capillary can also be filled with a gel, which eliminates the electroosmotic flow. Separation
is accomplished as in conventional gel electrophoresis but the capillary allows higher resolution,
greater sensitivity, and on-line detection.

Schematic of capillary electrophoresis

Electroosmotic flow
The surface of the silicate glass capillary contains negatively-charged functional groups that
attract positively-charged counterions. The positively-charged ions migrate towards the negative
electrode and carry solvent molecules in the same direction. This overall solvent movement is
called electroosmotic flow. During a separation, uncharged molecules move at the same velocity
as the electroosmotic flow (with very little separation). Positively-charged ions move faster and
negatively-charged ions move slower.
Schematic of the double layer on the capillary surface

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Definitions of Basic Electronic Quantities


Introduction
Electronic devices operate by the movement of electrons through conductors, e.g. wires, and
electronic components. The quantity, rate of flow, and driving force for electrons are described
by the following basic quantities.

Charge
Symbol: q, unit: coulomb (C)

Charge is an amount of electrons. One coulomb is the charge of 6x1018 electrons.

Current
Symbol: I, unit: ampere or amp (A)
Current is the rate of flow of charge, i. e., the number of coulombs flowing past a point per
second. One amp is equal to one coulomb per second.

Voltage
Symbol: V or E, unit: volt (V)

Voltage (also called potential, potential difference, potential drop, or electromotive force - EMF)
is the electronic potential energy between two points, and is the driving force that causes charge
to flow. One volt is defined as the potential difference that requires one joule of energy to move
one coulomb of charge.

Voltage is always measured relative to some other point in a circuit, e.g., the potential across a
resistor. Voltage measurements made at a single point in a circuit are made relative to the earth
(ground), which is assigned an "absolute" voltage of zero.

Impedance
Symbol: Z, unit: ohm ( )

Impedance is the degree to which an electronic component impedes the flow of current. In
general it is a frequency-dependent quantity.

The impedance of a resistor is also called its resistance. The impedance of capacitors and
inductors is also called their reactance.

Related Topics
The definitions of resistance, capacitance, and inductance are included with the discussion of
resistors, capacitors, and inductors, respectively.

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Ion Detectors
Channeltron
A channeltron is a horn-shaped continuous dynode structure that is coated on the inside with a
electron emissive material. An ion striking the channeltron creates secondary electrons that have
an avalanche effect to create more secondary electrons and finally a current pulse.

Daly detector
A Daly detector consists of a metal knob that emits secondary electrons when struck by an ion.
The secondary electrons are accelerated onto a scintillator that produces light that is then
detected by a photomultiplier tube.

Electron multiplier tube (EMT)


Electron multiplier tubes are similar in design to photomultiplier tubes. They consist of a series
of biased dynodes that eject secondary electrons when they are struck by an ion. They therefore
multiply the ion current and can be used in analog or digital mode.

Faraday cup
A Faraday cup is a metal cup that is placed in the path of the ion beam. It is attached to an
electrometer, which measures the ion-beam current. Since a Faraday cup can only be used in an
analog mode it is less sensitive than other detectors that are capable of operating in pulse-
counting mode.

Microchannel plate
A microchannel plate (MCP) consists of an array of glass capillaries (10-25 � m inner diameter)
that are coated on the inside with a electron-emissive material. The capillaries are biased at a
high voltage and like the channeltron, an ion that strikes the inside wall one of the capillaries
creates an avalanche of secondary electrons. This cascading effect creates a gain of 103 to 104
and produces a current pulse at the output.
Schematic of a microchannel plate

Microchannel plates (MCP) are also used as an intensifier for low-intensity light detection with
array detectors.

Related topics
 Introduction to mass spectrometry

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Charge-Coupled Devices (CCD)


Introduction
A CCD is an integrated-circuit chip that contains an array of capacitors that store charge when
light creates e-hole pairs. The charge accumulates and is read in a fixed time interval. CCDs are
used in similar applications to other array detectors such as photodiode arrays, although the CCD
is much more sensitive for measurement of low light levels.
Schematic of a CCD

Related Topics
 Optics
 Optical Materials
 Other optical detectors

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Introduction to Equilibrium
Introduction
Equilibrium is the condition at which a system is not changing. State variables such as
temperature and pressure are constant, the number of phases is not changing, and the
concentrations of the components of the system are not changing. Reactions are still occurring on
the microscopic scale, but the macroscopic concentrations are not changing.

When we say a system is at equilibrium we always mean that it is in a thermodynamic


equilibrium. A system might be kinetically stable or metastable, but not at equilibrium. A
balloon containing a mixture of H2 and O2 at room temperature is not in equilibrium. However, it
does not explode without a spark. Similarly, equilibrium and a "steady state" are not necessarily
the same thing. An open system in which reactants are entering and products are leaving a
reactor can be in a steady state but not at equilibrium.
Equilibrium is described quantitatively by the equilibrium constant. The related reaction quotient
provides a quantitative measure of how far a system is from equilibrium.

Specific Chemical Equilibria


A chemical specie will always exist in equilibrium with other forms of itself. The other forms
may exist in undetectable amounts but they are always present. These other forms arise due to
the natural disorder of nature that we call entropy (it's impossible to be perfect). As an example,
pure water consists of the molecular compound and dissociated ions that exist together in
equilibrium:

H2O(l) H+(aq) + OH-(aq)

The (l) subscript refers to the liquid state, and the (aq) subscript refers to ions in aqueous
solution.

More details are available for the following classifications of chemical equilibria:

 Acids and Bases - Kw, Ka, and Kb.


 Precipitation - Solubility of insoluble salts, Ksp.
 Complexation - Formation of complexes between metal ions and ligands, Kf.

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Chemiluminescence Spectroscopy
Introduction
Chemiluminescence, like atomic emission spectroscopy (AES), uses quantitative measurements
of the optical emission from excited chemical species to determine analyte concentration;
however, unlike AES, chemiluminescence is usually emission from energized molecules instead
of simply excited atoms. The bands of light determined by this technique emanate from
molecular emissions and are therefore broader and more complex then bands originating from
atomic spectra. Furthermore, chemiluminescence can take place in either the solution or gas
phase, whereas AES is almost strictly as gas phase phenomenon.
Though liquid phase chemiluminescence plays a significant role in laboratories using this
analytical technique (often in conjunction with liquid chromatography), we will concentrate on
gas phase chemiluminescence reactions since the instrumental components are somewhat
simpler. These detectors are also often used as detectors for gas chromatography.

Like fluorescence spectroscopy, chemiluminescence's strength lies in the detection of


electromagnetic radiation produced in a system with very low background. And on top of this,
because the energy necessary to excite the analytes to higher electronic, vibrational, and
rotational states (from which they can decay be emission) does not come from an external light
source like a laser or lamp, the problem of excitation source scattering is completely avoided.
The major limitation to the detection limits achievable by chemiluminescence involves the dark
current of the photomultiplier (PMT) necessary to detect the analyte light emissions.

If the excitation energy for analytes in chemiluminescence doesn't come from a source lamp or
laser, where does it come from? The energy is produced by a chemical reaction of the analyte
and a reagent. An example of a reaction of this sort is shown below:

A chemiluminescence reaction

In gas phase chemiluminescence, the light emission (represented as Planck's constant times nu-
the light's frequency) is produced by the reaction of an analyte (dimethyl sulfide in the above
example) and a strongly oxidizing reagent gas such as fluorine (in the example above) or ozone,
for instance. The reaction occurs on a time scale such that the production of light is essentially
instantaneous; therefore, most analytical systems simply mix analytes and the reagent in a small
volume chamber directly in front of a PMT. If the analytes are eluting from a gas
chromatographic column then the end of the column is often fed directly into the reaction
chamber itself. Since as much of the energy released by the reaction should (in the analyst's eye)
be used to excite as many of the analyte molecules as possible, loss of energy via gas phase
collisions is undesirable, and therefore a final consideration is that the gas pressure in the
reaction chamber be maintained at a low pressure (~ 1 torr) by a vacuum pump in order to
minimize the effects of collisional deactivation.

It must be stated that the ambiguous specification of "products" in the above reaction is often
necessary because of the nature and complexity of the reaction. In some reactions, the
chemiluminescent emitters are relatively well known. In the above reaction the major emitter is
electronically and vibrationally excited HF; however, in the same reaction, other emitters have
been determined whose identities are not known and these also contribute to the total light
detected by the PMT.

To the analytical chemist the ambiguity about the actual products in the reaction is, in most case,
not important. All the analyst cares about is the sensitivity of the instrument (read detection
limits for target analytes), its selectivity-that is, response for an analyte as compared to an
interfering compound, and the linear range of response.

Here is a schematic of the components necessary for a gas phase chemiluminescence detector
interfaced to a capillary gas chromatograph.

Schematic of a GC chemiluminescence detector

Related Topics
 Chemiluminescence Home Page at SHSU

These notes were written by Dr. Thomas G. Chasteen at Sam Houston State University,
Huntsville, Texas 77341.

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Chromatography
Introduction
Chromatography is a separations method that relies on differences in partitioning behavior
between a flowing mobile phase and a stationary phase to separate the the components in a
mixture.

A column (or other support for TLC, see below) holds the stationary phase and the mobile phase
carries the sample through it. Sample components that partition strongly into the stationary phase
spend a greater amount of time in the column and are separated from components that stay
predominantly in the mobile phase and pass through the column faster.

As the components elute from the column they can be quantified by a detector and/or collected
for further analysis. An analytical instrument can be combined with a separation method for on-
line analysis. Examples of such "hyphenated techniques" include gas and liquid chromatography
with mass spectrometry (GC-MS and LC-MS), Fourier-transform infrared spectroscopy (GC-
FTIR), and diode-array UV-VIS absorption spectroscopy (HPLC-UV-VIS).

Specific chromatographic methods:


Gas chromatography (GC)
Applied to volatile organic compounds. The mobile phase is a gas and the stationary
phase is usually a liquid on a solid support or sometimes a solid adsorbent.
High-performance liquid chromatography (HPLC)
A variation of liquid chromatography that utilizes high-pressure pumps to increase the
efficiency of the separation.
Liquid chromatography (LC)
Used to separate analytes in solution including metal ions and organic compounds. The
mobile phase is a solvent and the stationary phase is a liquid on a solid support, a solid, or
an ion-exchange resin.
Size-exclusion chromatography (SEC)
Also called gel-permeation chromatography (GPC), the mobile phase is a solvent and the
stationary phase is a packing of porous particles.
Thin-layer chromatography (TLC)
A simple and rapid method to monitor the extent of a reaction or to check the purity of
organic compounds. The mobile phase is a solvent and the stationary phase is a solid
adsorbent on a flat support.

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Chromatography Theory
Introduction
The underlying principles that determine chromatographic separations are dynamic behaviors
that depends on partitioning and mass transport. These phenomena are too complex to model
directly, and chromatography theory consists of empirical relationships to describe
chromatographic columns and the separation of peaks in chromatograms.

Description of Chromatograms
The retention of an analyte by a column is described by the capacity factor, k', where:

k' = tr - tm
-------
tm
where tr is the time for the analyte to pass through the column, and tm is the time for mobile
phase to pass through the column.

More info:

 Resolution of peaks in a chromatogram

Description of chromatographic columns


The resolution of chromatographic columns is described by the theoretical plate height, H, or the
number of theoretical plates, N. These two quantities are related by:
N=L/H
where L is the length of the column.

H and N provide useful measures to compare the performance of different columns for a given
analyte. Useful expressions are:
H = L W2 / 16 tr2
and
N = 16 (tr / W)2
where W is the width of the peak at its base.

More info:

 Golay Equation

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Complexation Reactions
Introduction
Consider the example of adding Cl- to a solution containing Ag+. As you might predict, a
precipitate forms because AgCl is an insoluble salt. What happens if we continue adding Cl- to
the solution containing the AgCl precipitate? Considering only Ksp and the common-ion effect,
we expect the solubility of AgCl to decrease continuously as the concentration of Cl- increases.
The solubility of AgCl decreases as the concentration of Cl- increases to 5x10-3 M where it
reaches a minimum. As [Cl-] increases above 5x10-3 M, the solubility of AgCl increases due to
the formation of AgCl2- and AgCl32-. Such a compound is called a complex, and can increase the
solubility of an insoluble salt as a complex forms.

Nomenclature
Ligand
Neutral or anionic species with unpaired electrons that can bond to a metal ion. Common
ligands are CN-, NH3, OH-, and halides.
Complex
An association of a central metal ion and surrounding ligands in solution - also called
coordination complex.
Coordination number
The number of bonds with the central metal ion, usually 2, 4, or 6.
Chelate
A specific type of complex in which at least one ligand contains more than one atom with
unpaired electrons so it can make multiple bonds with the central metal ion. Ligands that
make two bonds are called bidendate, ligand that make three bonds are tridendate, and so
on.

Examples
Metals with oxidation states of +1, +2, +3, or +4 can exist as complexes in water. Although we
discuss the metal concentration in solution, the metal really exists as an aquo complex.

Note that metals can exist in higher oxidation states, but the charge density is so high that they
do not exist as complexes in solution. They form oxyanions such as:
 MnO4-
 CrO42-
 Cr2O72-

As an example, what is present when Cu(NO3)2 is added to water?

We have Cu2+ and NO3- in solution. The NO3- is a spectator ion and we don't expect it to take
part in any equilibrium. Although we discuss [Cu2+], the Cu2+ probably exists as a tetra-aquo
complex Cu(H2O)42+. Water has two lone pairs of electrons on the oxygen and can form
complexes with transition metal ions. We can think of complexes in solution being in
competitive equilibria with other species. If NH3 is added, a Cu(NH3)42+ complex forms because
the NH3 complexes with Cu2+ more strongly than does water.

Ru(bpy)32+

tris(bipyridyl)ruthenium consists of a central ruthenium (green) surrounded by three bipyridyl


ligands. The nitrogen atoms (blue) have lone pairs of electrons to donate to empty orbitals on the
ruthenium to form the complex bonds. Stable complexes form for the ruthenium ion in both the
2+ and 3+ oxidation states. The charge of the central ion is not as critical as the overlap of lone
pairs of electrons with empty orbitals on the metal for the stability of complexes.

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Complexometric Titrations
Introduction
Recall that titration is the quantitative measurement of an analyte in solution by reacting it
completely with a standardized reagent. Complexes form in a fixed stoichiometry so a standard
solution of a ligand can be used to titrate a metal ion in solution. Similarly, a standard solution of
a metal ion can serve as the titrant for a species that acts as a ligand.

Ethylenediaminetetraacetic acid (EDTA) is a common chelate because it makes 6 bonds with


metal ions to form 1:1 complexes with large formation constants. The fully protonated form of
EDTA is:

CH2COOH CH2COOH
\ /
:N-CH2CH2-N:
/ \
CH2COOH CH2COOH

The two nitrogen atoms can donate their lone pairs to form two bonds and the four -OH groups
can lose thier protons to form four more bonds to the metal.

Kf Values for Some EDTA Complexes


Metal Name Kf
Ag+ silver 2.1x107
Al3+ aluminum 1.3x1016
Ba2+ barium 5.8x107
Ca2+ calcium 5.0x1010
Cd2+ cadmium 2.9x1016
Co2+ cobalt 2.0x1016
Fe2+ iron(II) 2.1x1014
Fe3+ iron(III) 1x1025
Hg2+ mercury 6x1021
Ni2+ nickel 4.2x1018
Pb2+ lead 1.1x1018
Zn2+ zinc 3.2x1016

Calmagite Indicator for EDTA Titrations


Calmagite indicator has two -OH groups with acidic protons. The color of calmagite changes
depending on whether or not these protons are present. At pH=10 one proton is present and the
color of the indicator is blue. A calcium or magnesium ion can displace both protons to form a
calmagite-metal complex, which has a red color. Ca2+ and Mg2+ can be titrated using EDTA as
the titrant and calmagite indicator because the EDTA binds Ca2+ and Mg2+ more strongly than
the indicator. At the endpoint, the EDTA will bind all of the metal, leaving the calmagite with no
metal ions. A solution containing calmagite will turn from red (or purple very near the endpoint)
to blue.

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Measures of Precision
Introduction
The following quantities are quantitative measures of precision. All of the equations below
provide precision measures for a limited number of repetitive measurements, i.e., between 2 and
20.

These quantities provide a measure of the uncertainty in a mean value determined from a series
of repetitive measurements. The mean or average, , is calculated from:

Where N is the number of measurements and xi is each individual measurement. is sometimes


called the sample mean to differentiate it from the true or population mean, µ. The formula for µ
is the same as above, but N must be at least 20 measurements.

Standard Deviation
The standard deviation, s, is a statistical measure of the precision for a series of repetitive
measurements. The advantage of using s to quote uncertainty in a result is that it has the same
units as the mean value. Under a normal distribution, ± one standard deviation encompasses 68%
of the measurements and ± two standard deviations encompasses 96% of the measurements. It is
calculated from:
Where N is the number of measurements, xi is each individual measurement, and is the mean
of all measurements. The quantity (xi - ) is called the "residual" or the "deviation from the
mean" for each measurement. The quantity (N -1) is called the "degrees of freedom" for the
measurement.

Relative Standard Deviation


The relative standard deviation (RSD) is useful for comparing the uncertainty between different
measurements of varying absolute magnitude. The RSD is calculated from the standard
deviation, s, and is commonly expressed as parts per thousand (ppt) or percentage (%):

The %-RSD is also called the "coefficient of variance" or CV.

Confidence Limits
The confidence limits are another statistical measure of the precision for a series of repetitive
measurements. They are calculated from the standard deviation using:

You would say that with some confidence, for example 95%, the true value is between the
confidence limits. The t term is taken from a table for the number of degrees of freedom and the
degree of confidence desired.

t values for finding confidence limits


D.F. 90% 95% 99%
1 6.31 12.71 63.66
2 2.92 4.30 9.93
3 2.35 3.18 5.84
4 2.13 2.78 4.60
5 2.01 2.57 4.03
6 1.94 2.45 3.71
7 1.90 2.37 3.50
15 1.75 2.13 2.95
1.65 1.96 2.58

You might also encounter the term "confidence interval". The confidence interval is the span
between the confidence limits:

Other Measures of Precision


The quantitative measures of precision described above are the most common for reporting
analytical results. You might encounter other measures of precisions, and several other quantities
are listed here for completeness.

standard error:

variance:

The advantage of working with variance is that variances from independent sources of variation
may be summed to obtain a total variance for a measurement.
All of the equations above are for quantitating the precision of a relatively small numbers of
replicate measurements. For 20 or more measurements, the true or population standard deviation,
, is:

Related topics:
 data handling

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Physical Constants
ao Bohr radius 0.5291771x10-10 m
c speed of light (vacuum) 2.997925x108 m/s
e electron charge 1.602189x10-19 C
E permittivity of vacuum 8.854188x10-12 C2/J m
F Faraday constant 96485.34 C/mol
h Planck's constant 6.626176x10-34 J s
u permeability of vacuum 1.256637x10-6 H/m
me electron rest mass 9.109534x10-31 kg
mp proton rest mass 1.672648x10-27 kg
NA Avogadro's number 6.022045x1023 /mol
R molar gas constant 8.31447 J/mol·K

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Continuous-Wave Nuclear Magnetic
Resonance (NMR) Spectroscopy
Introduction
Continuous-wave NMR spectrometers have largely been replaced with pulsed FT-NMR
instruments. However due to the lower maintenance and operating cost of cw instruments, they
are still commonly used for routine 1H NMR spectroscopy at 60 MHz. (Low-resolution cw
instruments require only water-cooled electromagnets instead of the liquid-He-cooled
superconducting magnets found in higher-field FT-NMR spectrometers.)

Instrumentation
A cw-NMR spectrometer consists of a control console, magnet, and two orthogonal coils of wire
that serve as antennas for radiofrequency (RF) radiation. One coil is attached to an RF generator
and serves as a transmitter. The other coil is the RF pick-up coil and is attached to the detection
electronics.

Since the two coils are orthogonal, the pick-up coil cannot directly recieve any radiation from the
generator coil. When a nucleus absorbs RF radiation, it can become reoriented due to its normal
movement in solution and re-emit the RF radiation is a direction that can be recieved by the pick-
up coil. This orthogonal coil arrangement greatly increases the sensitivity of NMR spectroscopy,
similar to optical fluorescence.

Spectra are obtained by scanning the magnet and recording the pick-up coil signal on paper at the
control console.

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Coulometry
Introduction
Coulometry is an analytical method for measuring an unknown concentration of an analyte in
solution by completely converting the analyte from one oxidation state to another. Coulometry is
an absolute measurement similar to gravimetry or titration and requires no chemical standards or
calibration. It is therefore valuable for making absolute concentration determinations of
standards.

Coumetry uses a constant current source to deliver a measured amount of charge. One mole of
electrons is equal to 96,485 coulombs of charge, and is called a faraday.

Schematic of a coulometric cell

Coulometric Titration
Due to concentration polarization it is very difficult to completely oxidize or reduce a chemical
species at an electrode. Coulometry is therefore usually done with an intermediate reagent that
quantitatively reacts with the analyte. The intermediate reagent is electrochemically generated
from an excess of a precursor so that concentration polarization does not occur. An example is
the electrochemical oxidation of I- (the precursor) to I2 (the intermediate reagent). I2 can then be
used to chemically oxidize organic species such as ascorbic acid.

The point at which all of the analyte has been converted to the new oxidation state is called the
endpoint and is determined by some type of indicator that is also present in the solution. For the
coulometric titration of ascorbic acid, starch is used as the indicator. At the endpoint, I2 remains
in solution and binds with the starch to form a dark purple complex.

The analyte concentration is calculated from the reaction stoichiometry and the amount of charge
that was required to produce enough reagent to react with all of the analyte.

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Definitions of Basic Electronic Quantities
Introduction
Electronic devices operate by the movement of electrons through conductors, e.g. wires, and
electronic components. The quantity, rate of flow, and driving force for electrons are described
by the following basic quantities.

Charge
Symbol: q, unit: coulomb (C)

Charge is an amount of electrons. One coulomb is the charge of 6x1018 electrons.

Current
Symbol: I, unit: ampere or amp (A)

Current is the rate of flow of charge, i. e., the number of coulombs flowing past a point per
second. One amp is equal to one coulomb per second.

Voltage
Symbol: V or E, unit: volt (V)

Voltage (also called potential, potential difference, potential drop, or electromotive force - EMF)
is the electronic potential energy between two points, and is the driving force that causes charge
to flow. One volt is defined as the potential difference that requires one joule of energy to move
one coulomb of charge.

Voltage is always measured relative to some other point in a circuit, e.g., the potential across a
resistor. Voltage measurements made at a single point in a circuit are made relative to the earth
(ground), which is assigned an "absolute" voltage of zero.

Impedance
Symbol: Z, unit: ohm ( )

Impedance is the degree to which an electronic component impedes the flow of current. In
general it is a frequency-dependent quantity.

The impedance of a resistor is also called its resistance. The impedance of capacitors and
inductors is also called their reactance.

Related Topics
The definitions of resistance, capacitance, and inductance are included with the discussion of
resistors, capacitors, and inductors, respectively.

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Current-to-Voltage Conversion
Introduction
The output from many detectors is a current (some number of electrons / second). It is desirable
to convert this current signal to a voltage to avoid capacitive charging effects. The simplest way
to do so is to drop the current across a load resistor and measure the voltage.

Schematic of a I to V conversion using a resistor:

This simple current-to-voltage converter has some disadvantages that can be avoided by using an
op-amp.
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Cyclic Voltammetry (CV)


Introduction
Cyclic voltammetry (CV) is an electrolytic method that uses microelectrodes and an unstirred
solution so that the measured current is limited by analyte diffusion at the electrode surface. The
electrode potential is ramped linearly to a more negative potential, and then ramped in reverse
back to the starting voltage. The forward scan produces a current peak for any analytes that can
be reduced through the range of the potential scan. The current will increase as the potential
reaches the reduction potential of the analyte, but then falls off as the concentration of the
analyte is depleted close to the electrode surface. As the applied potential is reversed, it will
reach a potential that will reoxidize the product formed in the first reduction reaction, and
produce a current of reverse polarity from the forward scan. This oxidation peak will usually
have a similar shape to the reduction peak. The peak current, ip, is described by the Randles-
Sevcik equation:

ip = (2.69x105) n3/2 A C D1/2 v1/2

where n is the number of moles of electrons transferred in the reaction, A is the area of the
electrode, C is the analyte concentration (in moles/cm3), D is the diffusion coefficient, and v is
the scan rate of the applied potential.

The potential difference between the reduction and oxidation peaks is theoretically 59 mV for a
reversible reaction. In practice, the difference is typically 70-100 mV. Larger differences, or
nonsymmetric reduction and oxidation peaks are an indication of a nonreversible reaction. These
parameters of cyclic voltammograms make CV most suitable for characterization and
mechanistic studies of redox reactions at electrodes.

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Ion Detectors
Channeltron
A channeltron is a horn-shaped continuous dynode structure that is coated on the inside with a
electron emissive material. An ion striking the channeltron creates secondary electrons that have
an avalanche effect to create more secondary electrons and finally a current pulse.

Daly detector
A Daly detector consists of a metal knob that emits secondary electrons when struck by an ion.
The secondary electrons are accelerated onto a scintillator that produces light that is then
detected by a photomultiplier tube.

Electron multiplier tube (EMT)


Electron multiplier tubes are similar in design to photomultiplier tubes. They consist of a series
of biased dynodes that eject secondary electrons when they are struck by an ion. They therefore
multiply the ion current and can be used in analog or digital mode.

Faraday cup
A Faraday cup is a metal cup that is placed in the path of the ion beam. It is attached to an
electrometer, which measures the ion-beam current. Since a Faraday cup can only be used in an
analog mode it is less sensitive than other detectors that are capable of operating in pulse-
counting mode.

Microchannel plate
A microchannel plate (MCP) consists of an array of glass capillaries (10-25 � m inner diameter)
that are coated on the inside with a electron-emissive material. The capillaries are biased at a
high voltage and like the channeltron, an ion that strikes the inside wall one of the capillaries
creates an avalanche of secondary electrons. This cascading effect creates a gain of 103 to 104
and produces a current pulse at the output.
Schematic of a microchannel plate

Microchannel plates (MCP) are also used as an intensifier for low-intensity light detection with
array detectors.

Related topics
 Introduction to mass spectrometry

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Introduction to Data Acquisition (DAQ)


Introduction
The simplest way to store data is to record it on paper with either a strip-chart recorder or an x-y
plotter. For greater utility, most modern analytical instruments digitize data in digital format for
subsequent data storage, analysis, and presentation. For some types of instruments, such as
Fourier-transform-based spectrometers, digitized data is necessary for the data manipulation to
extract the spectrum from the raw data. Many instruments digitize and store data in memory for
subsequent transfer to a computer file. Other instruments will use a software program to control
an instrument and digitize the analytical signal through a computer data acquisition (DAQ)
interface.

Most analytical signals are an analog voltage from a transducer. This signal must be digitized to
discrete data points without losing analytical information. The important parameters for
digitizing data are the resolution of the analog-to-digital converter and the sampling rate.
The resolution depends on the number of bits in the digital representation. For example, an 8-bit
converter has a resolution of 28 or 1 part in 256. If the input range of the analog-to-digital
converter was 0 to 10 V, the smallest detectable voltage would be 0.04 V. 0.04 V is also the
minimum discernable difference between two voltage measurements.

The sampling rate must be greater than two times the highest frequency in the analytical signal to
avoid aliasing the data. Signals at frequencies greater than the sampling rate can appear to be at
lower frequencies.

Data Transfer
Data that is stored digitally in an instrument can be transferred to a computer via an RS-232
serial port, general-purpose interface bus (GPIB), or a proprietary protocol. The advantage of
using the RS-232 port is that it is available on all computers. The disadvantage is that it is not a
fast transfer since it is a serial transfer mode. Newer standards such as the universal serial bus
(USB) are faster but only available on newer instruments. The GPIB protocol uses 24 parallel
data lines to provide fast data transfer, but it requires a dedicated plug-in interface board in the
computer. Some instruments are now available with a DOS-compatible floppy disk drive. The
disk drive makes file storage and transfer easy, but can be cumbersome for large numbers of files
and for very large individual data files.

Computer DAQ
Voltages can be digitized into computer memory through plug-in DAQ boards that contain
analog-to-digital converters or stand-alone interfaces that transfer data to the computer through a
serial port. Many of the commercial DAQ boards also support digital and trigger inputs, as well
as analog and digital outputs for integrated data acquisition and instrument control. A variety of
software packages support the commercially available DAQ boards for data acquisition and
instrument control. National Instruments, Inc. (http://www.natinst.com) sells a wide range of
DAQ boards and LabViewTM software for sophisticated instrument control, data acquisition, and
data analysis. Vernier Software, Inc. (http://www.vernier.com) sells a variety of probes for
biological, chemical, and physical measurements, computer and calculator interfaces, and data
logging software.

Related Topics
 Index of detection electronics
 Introduction to electronics
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Data Handling
Introduction
Since analytical chemistry is the science of making quantitative measurements, it is important
that raw data is manipulated and reported correctly to give a realistic estimate of the uncertainty
in a result.

Simple data manipulations may only require keeping track of significant figures. More
complicated calculations require propagation-of-error methods.

The uncertainity in a result can be categorized into random error and systematic error.

See the statistical formula document for more quantitative descriptions of describing and testing
data sets.

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de Broglie Equation
Introduction
Moving particles; such as electrons, protons, and neutrons; have wave properties as described by
the de Broglie equation:

=h/p

where is wavelength, h is Planck's constant (6.62618x10-34 J·s), and p is the momentum of the
particle. Beams of particles can therefore show wave effects such as diffraction.
Related topics
 Electromagnetic Radiation
 Introduction to Diffraction

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Radiation Detectors
Introduction
Detectors convert light energy to an electrical signal. In spectroscopy, they are typically placed
after a wavelength separator to detect a selected wavelength of light. Different types of detectors
are needed for different parts of the electromagnetic spectrum. The detectors are listed in order of
their approximate wavelength ranges from shorter wavelength (higher energy photons) to longer
wavelength (lower energy photons).

Index of radiation detectors


 X-ray and gamma-ray detectors
 Photomultiplier tube (PMT)
 Charge-coupled detector array (CCD)
 Photodiode array (PDA)
 Visible and infrared semiconductor detectors (photodiodes and photovoltaics)

Related Topics
 Optics
 Optical Materials

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Gas Chromatography (GC) Detectors


Introduction
After the components of a mixture are separated using gas chromatography, they must be
detected as they exit the GC column. The links listed below provide the details of some specific
GC detectors. The thermal-conductivity (TCD) and flame-ionization (FID) detectors are the two
most common detectors on commercial gas chromatographs. The requirements of a GC detector
depends on the separation application. For example, one analysis might require a detector that is
selective for chlorine-containing molecules, another analysis might require a detector that is non-
destructive so that the analyte can be recovered for further spectroscopic analysis.

Specific GC detectors
Atomic-emmision detector (AED)

Chemiluminescence detector

Electron-capture detector (ECD)


The ECD is as sensitive as the FID but has a limited dynamic range and finds its greatest
application in analysis organic molecules that contain electronegative functional groups,
such as halogens, phosphorous, and nitro groups.
Flame-ionization detector (FID)
The FID is extremely sensitive with a large dynamic range, its only disadvantage is that it
destroys the sample.
Flame-photometric detector (FPD)

Mass spectrometer (MS)


Mass spectrometers provide structural information to identify the analyte in a
chromatographic peak.
Nitrogen-phosphorus detector (NPD)
A detector similar in design to an FID but with selectivity for compounds containing
nitrogen and phosphorus.
Photoionization detector (PID)

Thermal conductivity detector (TCD)


The TCD is not as sensitive as other dectectors but it is non-specific and non-destructive.

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Introduction to Detection Electronics


Introduction
An analytical signal usually comes from some type of light detector, ion detector, or sensor. To
be useful this analytical signal must often be converted from a current to a voltage, averaged, or
manipulated, and stored.

Detection Electronics
 Current-to-voltage conversion
 Gated integrator
 Lock-in amplifier
 Oscilloscope
o introduction
o digital oscilloscope
 Pulse counting (photon counting)
 Transient recorder

Related Topics
 Introduction to electronics
 Introduction to computer data acquisition

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Ground State of a Diatomic Molecule


Introduction
Two atoms that can form a bond will do so to create a diatomic molecule when they approach
each other closely. We describe the energy minimum with a potential energy curve, called a
potential well.

Morse Potential
The potential energy, V(R), of a diatomic molecule can be described by the Morse potential:

where De is the well depth, R is internuclear distance, Re is the equlibrium internuclear distance
(bond length), and

e is the vibrational constant and µ is the reduced mass.

The following figure shows the ground state potential well of the H2 molecule. The curve is
calculated from the Morse potential and the energy levels are calculated using the harmonic
oscillator model with the first anharmonic correction.
Do is the dissociation energy, which is slightly different from the well depth, De. The vibrational
energy levels in this plot are calculated using the harmonic oscillator model:

where v is the vibrational quantum number, v = 0,1,2,..., and xe and ye are the first and second
anharmonicity constants, respectively. The v = 0 level is the vibrational ground state.

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Differential Pulse Polarography (DPP)


Introduction
Differential Pulse Polarography is a polarographic technique that uses a series of discrete
potential steps rather than a linear potential ramp to obtain the experimental polarogram. Many
of the experimental parameters for differential pulse polarography are the same as with normal
pulse polarography (for example accurately timed drop lifetimes, potential step duration of 50 -
100 ms at the end of the drop lifetime). Unlike Normal Pulse Polarography, however, each
potential step has the same amplitude, and the return potential after each pulse is slightly
negative of the potential prior to the step.

Differential pulse polarography

In this manner, the total waveform applied to the DME is very much like a combination of a
linear ramp with a superimposed square wave. The differential pulse polarogram is obtained by
measuring the current immediately before the potential step, and then again just before the end of
the drop lifetime. The analytical current in this case is the difference between the current at the
end of the step and the current before the step (the differential current). This differential current
is then plotted vs. the average potential (average of the potential before the step and the step
potential) to obtain the differential pulse polarogram. Because this is a differential current, the
polarogram in many respects is like the differential of the sigmoidal normal pulse polarogram.
As a result, the differential pulse polarogram is peak shaped.

Differential pulse polarography has even better ability to discriminate against capacitive current
because it measures a difference current (helping to subtract any residual capacitive current that
remains prior to each step). Limits of detection with Differential Pulse Polarography are 10-8 -
10-9 M.

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Thermal Analysis
Introduction
Thermal analytical methods monitor differences in some sample property as the temperature
increases, or differences in temperature between a sample and a standard as a function of added
heat. These methods are usually applied to solids to characterize the materials.

Thermogravimetry (TG)
Thermogravimetry is the measurement of the mass of a sample as the temperature increases. This
method is useful for determining sample purity and water, carbonate, and organic content; and
for studying decomposition reactions.

Differential Thermal Analysis (DTA)


Differential thermal analysis is the measurement of the difference in temperature between a
sample and a reference as heat is applied to the system. This method is sensitive to endothermic
and exothermic processes including: phase transitions, dehydration, and decomposition, redox, or
solid-state reactions.

Differential Scanning Calorimetry (DSC)


Differential scanning calorimetry independently measures the rate of heat flow to a sample and a
standard that are at the same temperature. Data is taken by monitoring the differential heat flow
as a function of temperature. DSC is useful to make the same measurements as DTA and has the
added capability to measure heat capacities.

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Thermal Analysis
Introduction
Thermal analytical methods monitor differences in some sample property as the temperature
increases, or differences in temperature between a sample and a standard as a function of added
heat. These methods are usually applied to solids to characterize the materials.

Thermogravimetry (TG)
Thermogravimetry is the measurement of the mass of a sample as the temperature increases. This
method is useful for determining sample purity and water, carbonate, and organic content; and
for studying decomposition reactions.

Differential Thermal Analysis (DTA)


Differential thermal analysis is the measurement of the difference in temperature between a
sample and a reference as heat is applied to the system. This method is sensitive to endothermic
and exothermic processes including: phase transitions, dehydration, and decomposition, redox, or
solid-state reactions.

Differential Scanning Calorimetry (DSC)


Differential scanning calorimetry independently measures the rate of heat flow to a sample and a
standard that are at the same temperature. Data is taken by monitoring the differential heat flow
as a function of temperature. DSC is useful to make the same measurements as DTA and has the
added capability to measure heat capacities.

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Diffraction
Introduction
Diffraction is a wave property of electromagnetic radiation that causes the radiation to bend as it
passes by an edge or through an aperture. Diffraction effects increase as the physical dimension
of the aperture approaches the wavelength of the radiation. Diffraction of radiation results in
interference that produces dark and bright rings, lines, or spots, depending on the geometry of the
object causing the diffraction. Common interference effects for visible light are the rainbow
pattern produced by an oil film on wet pavement and the diffraction of light from a narrow slit or
a diffraction grating.

Diffraction Methods
A certain wavelength of radiation will constructively interfere when partially reflected between
surfaces that produce a path difference equal to an integral number of wavelengths. This
condition is described by the Bragg law:
n = 2dsin
where n is an integer, lambda is the wavelength of the radiation, d is the spacing between
surfaces, and theta is the angle between the radiation and the surfaces. This relation demonstrates
that interference effects are observable only when radiation interacts with physical dimensions
that are approximately the same size as the wavelength of the radiation.

Interference of radiation between atomic planes in a crystal

These interference effects are useful for determining dimensions in solid materials, and therefore
crystal structures. Since the distances between atoms or ions is on the order of 10-10 m (1 Å),
diffraction methods require radiation in the X-ray region of the electromagnetic spectrum, or
beams of electrons or neutrons with a similar wavelength. Electrons and neutrons are commonly
thought of as particles, but they have wave properties with the wavelength depending on the
energy of the particles as described by the de Broglie equation. The three diffraction methods
have different properties that are described in more detail in separate documents. For example,
the penetration depths of the three types of beams are quite different:
neutrons > X-rays > electrons.
Schematic of crystal-structure determination by diffraction

Related Topics
 electron diffraction
 neutron diffraction
 X-ray diffraction

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Digital Oscilloscope
Introduction
Digital oscilloscopes serve the same purpose as analog oscilloscopes but convert the analog
voltage input to digital values. These values are stored in memory allowing the capture and
continuous display of one-time events, and the summing and averaging of repetitive signals to
improve the signal-to-noise ratio of the signal.

Single and averaged traces on a digital oscilloscope


Related Topics
 Index of detection electronics
 Introduction to electronics
 Introduction to data acquisition

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Diodes
Introduction
A diode is a passive electronic component that allows current to flow in only one direction.
There are several types of diodes, as listed in the circuit symbol diagram. The arrow in the
diagram points in the direction of "easy" current flow.

Circuit symbol

Applications
Diodes are often used for rectifying an ac voltage to a dc voltage.

Photodiodes are a special type of diode that allows current to flow only when light strikes the
photodiode. These components are useful as light detectors.

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Lamps
Introduction
Lamps convert electrical energy into radiation. Different designs and materials are needed to
produce light in different parts of the electromagnetic spectrum. The following sections describe
several different types of lamps that are useful in spectroscopy.

Blackbody Sources
A hot material, such as an electrically-heated filament in a light bulb, emits a continuum
spectrum of light. The spectrum is approximated by Planck's radiation law for blackbody
radiators:

B = {2h 3/c2}{1/exp(h /kT)-1}


where h is Planck's constant, is frequency, c is the speed of light, k is the Boltzmann constant,
and T is temperature in K.

The most common incandescent lamps and their wavelength ranges are:
tungsten filament lamps : 350 nm - 2.5 µm
glowbar : 1 - 40 µm
Nernst glower : 400 nm - 20 µm

Tungsten lamps are used in visible and near-infrared (NIR) absorption spectroscopy and the
glowbar and Nernst glower are used for infrared spectroscopy.

Discharge Lamps
Discharge lamps, such as neon signs, pass an electric current through a rare gas or metal vapor to
produce light. The electrons collide with gas atoms, exciting them to higher energy levels which
then decay to lower levels by emitting light. Low-pressure lamps have sharp line emission
characteristic of the atoms in the lamp, and high-pressure lamps have broadened lines
superimposed on a continuum.

Common discharge lamps and their wavelength ranges are:


hydrogen or deuterium : 160 - 360 nm
mercury : 253.7 nm, and weaker lines in the near-uv and visible
Ne, Ar, Kr, Xe discharge lamps : many sharp lines throughout the near-uv to near-IR
xenon arc : 300 - 1300 nm

Deuterium lamps are the uv source in UV-vis absorption spectrophotometers. The sharp lines of
the mercury and rare gas discharge lamps are useful for wavelength calibration of optical
instrumentation. Mercury and xenon arc lamps are used to excite fluorescence.

Hollow-cathode Lamps
Hollow-cathode lamps are a type of discharge lamp that produce narrow emission from atomic
species. They get their name from the cup-shaped cathode, which is made from the element of
interest. The electric discharge ionizes rare gas atoms, which are accelerated into the cathode and
sputter metal atoms into the gas phase. Collisions with gas atoms or electrons excite the metal
atoms to higher energy levels, which decay to lower levels by emitting light.

Schematic of a hollow-cathode lamp

Hollow-cathode lamps have become the most common light source for atomic absorption (AA)
spectroscopy. They are also sometimes used as an excitation source for atomic-fluorescence
spectroscopy (AFS).

Related Topics
 Optics
 Optical Materials

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Discontinous Electrophoresis
Introduction
Discontinous electrophoresis uses two gels that are buffered at different pHs. When proteins
migrate from one gel to the other they become concentrated into sharp bands, which produce
higher resolution than in conventional gel electrophoresis.

Schematic of discontinous electrophoresis separation

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Doppler-Free Laser Spectroscopy


Introduction
Doppler broadening arises from the random distribution of absorption (or emission) frequencies
of atoms (or molecules). The distribution of frequencies occurs because the atoms have a
distribution of velocities relative to the laser beam and are therefore Doppler shifted by:
w = wo � k * v
where w is the laser frequency, wo is the transition frequency, k is the wavevector of the
radiation, and v is the velocity of the atom. Removing Doppler broadening allows measurement
of the natural linewidth, and shows any underlying fine structure such as isotope shifts, hyperfine
splitting, and Zeeman splitting.
Saturation spectroscopy
Counterpropagating laser beams produce a Doppler-free saturation dip (Lamb dip) in the center
of a Doppler-broadened line. When the laser frequency is tuned off line center, one beam
interacts with +k*v atoms, while the beam propagating in the opposite direction interacts with -
k*v atoms. At the center of the Doppler line both laser beams interact with the same velocity
group (k*v=0, i.e., atoms moving perpendicular to the laser beams). When the laser intensity is
high enough to saturate the transition, the counterpropagating beam adds no additional excitation
of the k*v=0 atoms and the overall observed signal is less than that for the case when exciting
k*v atoms. This decrease in the signal appears as a narrow Lamb dip.

Two-photon absorption
For atoms or molecules with convenient two-photon transitions, the Doppler width can be
eliminated by using counterpropagating beams. In the atomic frame of reference, the two laser
beams appear at frequencies of wo(1- k*v/c) and wo(1+ k*v/c), where wo is the frequency
halfway to the two-photon level. The velocity dependence cancels out and the net result is that
all atoms will absorb photons with a total energy of the two-photon transition. Due to absorption
of two photons travelling in the same direction, this method will have some residual absorption
of the full Doppler width.

Related Topics
see also:

 laser spectroscopy
 high-resolution spectroscopy
 nonlinear spectroscopy

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Electrochemical Cells
Introduction
Consider the spontaneous reaction of Zn metal in a solution of Cu2+:

Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) Go = -212.6 kJ/mol

If we just dump the reactants (Zn metal and Cu2+) together, they react to produce Zn2+, Cu metal,
and heat. We can capture this energy by setting up an electrochemical cell to separate the two
half reactions.

Zn(s) Zn2+(aq) + 2e- Cu2+(aq) + 2e- Cu(s)

In this set-up Zn is being oxidized in one cell and Cu2+ is being reduced in the other cell. The Zn
electrode appears corroded due to loss of Zn into solution, and the Cu electrode is being plated
with Cu from solution. The salt bridge is a tube filled with a saturated KNO3 solution. It has frits
on the ends that prevent mixing of the solutions but allowing ions to pass through. As the cell
operates Zn2+ is produced in one cell and Cu2+ is removed from the other cell. Ions move through
the salt bridge to keep the individual cells electrically neutral.

The driving force is the same for the case of just mixing the reactants. By separating the two half
reactions, the electrons must travel through the wire and we can use the electrical energy. In the
sketch above the electrical energy powers a light bulb.

When we first set up this electrochemical cell and complete the circuit, we could measure a
voltage through the wire. As the reaction proceeds, the system approaches equilibrium and the
voltage would eventually go to zero.

Batteries are electrochemical cells that convert chemical energy to electrical energy. The
reactants in batteries are at non-equilibrium concentrations. As you use them, the reactants form
products to approach equilibrium and the voltage drops until the battery is no longer usable.

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Electrochemistry
Introduction
Electrochemistry encompasses chemical and physical processes that involve the transfer of
charge. Some examples are electroplating, iron oxidation (rusting), solar-energy conversion,
energy storage (batteries), photosynthesis, and respiration. Links to background documents on
redox chemistry are listed below.

Electroanalytical chemistry
There are two categories of electrochemical processes that are applied to quantitative
measurements:

1. potentiometry - measurement of a potential (voltage)


2. electrolytic methods - measurement involving a current

In both of these categories, an electrochemical measurement can be related to the concentration


of an analyte. See the Electrochemistry Index for links to specific electrochemical techniques.
Background on redox chemistry
 Redox introduction
 Electrochemical cells
 Balancing redox equations
 Standard reduction potentials
 Nernst equation
 Thermodynamics of redox reactions

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Electrolytic Methods
Introduction
Unlike potentiometry, where the free energy contained within the system generates the analytical
signal, electrolytic methods are an area of electroanalytical chemistry in which an external
source of energy is supplied to drive an electrochemical reaction which would not normally
occur. The externally applied driving force is either an applied potential or current. When
potential is applied, the resultant current is the analytical signal; and when current is applied, the
resultant potential is the analytical signal. Techniques which utilize applied potential are
typically referred to as voltammetric methods while those with applied current are referred to as
galvanostatic methods.

Voltammetric Methods
Voltammetry refers to the measurementof current that results from the application of potential.
Unlike potentiometry measurements, which employ only two electrodes, voltammetric
measurements utilize a three electrode electrochemical cell. The use of the three electrodes
(working, auxillary, and reference) along with the potentiostat instrument allow accurate
application of potential functions and the measurement of the resultant current. The different
voltammetric techniques that are used are distinguished from each other primarily by the
potential function that is applied to the working electrode to drive the reaction, and by the
material used as the working electrode. Common techniques to be discussed here include:
Hydrodynamic Voltammetry

 Polarography
 Normal-pulse polarography (NPP)
 Differential-pulse polarography (DPP)
 Cyclic voltammetry
 Anodic-stripping voltammetry

Time Based Techniques

 Chronoamperometry
 Chronocoulometry

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Electromagnetic Radiation
Introduction
Electromagnetic radiation consists of discrete packets
of energy, which we call photons. A photon consists of
an oscillating electric field component, E, and an
oscillating magnetic field component, M. The electric
and magnetic fields are orthogonal (perpendicular) to
each other, and they are orthogonal to the direction of
propogation of the photon. The electric and magnetic
fields of a photon flip direction as the photon travels.
We call the number of flips, or oscillations, that occur
in one second the frequency, . Frequency has the
units of oscillations per second, or simply s-1 (this unit
is given the name Hertz). If the electric and magnetic
fields of a photon could be recorded as the photon
traveled some distance, it would leave the trail of E and
M fields shown in the figure.

All photons (in a given, non-absorbing medium) travel at the same velocity, v. The physical
distance in the direction of propogation over which the electric and magnetic fields of a photon
make one complete oscillation is called the wavelength, , of the electromagnetic radiation. The
figure above shows the hypothetical history of a photon that has traveled the distance of one
wavelength. The relationship between the light velocity, wavelength, and frequency is:

v=

The electromagnetic nature of all photons is the same, but photons can have different
frequencies. The names we give electromagnetic radiation for different wavelength and
frequency ranges are listed in the electromagnetic spectrum document. The energy, E, of one
photon depends on its frequency of oscillation:

E=h = hv /

where h is Planck's constant (6.62618x10-34 J·s).

Velocity of light
Electromagnetic waves travel through a vacuum at a constant velocity of 2.99792x108 m/s,
which is known as the speed of light, c. The relationship between the speed of light, wavelength,
and frequency is:

c=

When light passes through other media, the velocity of light decreases. Since the energy of a
photon is fixed, the frequency of a photon does not change. Thus for a given frequency of light,
the wavelength must decrease as the velocity decreases.

The decrease in velocity is quantitated by the refractive index, n, which is the ratio of c to the
velocity of light in another medium, v:

n=c/v

Since the velocity of light is lower in other media than in a vacuum, n is


medium n*
always a number greater than one. The table lists the refractive index of
several examples. Refractive index is an intrinsic physical property of a air 1.0003
substance, and can be used to monitor purity or the concentration of a
solute in a solution. The refractive index of a material is measured with a water 1.333
refractometer, and is usually made versus air. If the precision warrants, 50%
the measurements can be corrected for vacuum. Note that the difference sucrose in 1.420
between nair and nvacuum is only significant in the fourth decimal place. water

For anisotropic materials, such as quartz crystals, light of different carbon


1.628
polarizations (see below) will experience different refractive indices. disulfide
These indices are called the ordinary refractive index, no, and the
extraordinary refractive index, ne. crystalline 1.544
quartz (no)
1.553
(ne)
diamond 2.417
*measured with 589.3
nm light

Polarization
An incoherent light source, such as the hot filament of a light bulb, consists of multiple,
randomly oriented light emitters, which produce electromagnetic waves with their electric-field
vector oriented in all directions. The resulting light emission is called unpolarized light.

Linearly (or plane) polarized light is light in which the electric-field vector is oscillating in only
one direction. Linearly polarized light is produced by isolating one orientation of the electric
field with a polarizer, or from lasers that contain polarized optical components.

Circularly polarized light is light in which the electric field vector is rotating around the axis of
light propogation. The electric field vector can rotate in either the right or left direction (as
viewed in the direction of light propogation), and the light is called right circularly polarized or
left circularly polarized, respectively.

Related topics
 Electromagnetic Spectrum
 Introduction to Spectroscopy

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Electromagnetic Spectrum
Introduction
For convenience in talking about electromagnetic radiation, we classify photons of different
energies into different spectral regions. The photons in all of these regions have the same
electromagnetic nature, but because of their very different energies they interact with matter very
differently. For example, the human eye can only detect radiation that is in the visible region of
the spectrum (hence the name). These photons are both transmitted by the lens of the human eye
and absorbed by the photoreceptors in the retina. There is no fundamental difference in the
nature of electromagnetic radiation of 350 nm versus 400 nm, other than our eyes can sense the
400-nm photons directly. A 350-nm photon is in the ultraviolet portion of the electromagnetic
spectrum. Some of the boundaries between spectral regions are not well-defined as between
ultraviolet and visible radiation.

Visible Spectrum
The visible region of the electromagnetic spectrum consists of photons with wavelengths from
approximately 400 to 700 nm. The short wavelength cutoff is due to absorption by the lens of the
eye and the long wavelength cutoff is due to the decrease in sensitivity of the photoreceptors in
the retina for longer wavelengths. Light at wavelengths longer than 700 nm can be seen if the
light source is intense.

Electromagnetic Spectrum
The following table lists the names of different spectral regions, the range of frequencies and
wavelengths in those regions, and the type of transition that can occur when a photon in these
spectral ranges interacts with matter.

Type of Frequency Range Wavelength


Type of Transition
Radiation (Hz) Range
gamma-rays 1020-1024 <1 pm nuclear
X-rays 1017-1020 1 nm-1 pm inner electron
ultraviolet 1015-1017 400 nm-1 nm outer electron
visible 4-7.5x1014 750 nm-400 nm outer electron
outer electron molecular
near-infrared 1x1014-4x1014 2.5 µm-750 nm
vibrations
infrared 1013-1014 25 µm-2.5 µm molecular vibrations
molecular rotations, electron spin
microwaves 3x1011-1013 1 mm-25 µm
flips*
radio waves <3x1011 >1 mm nuclear spin flips*

*for energy levels split by a magnetic field

Related topics
 Electromagnetic radiation
 Introduction to spectroscopy

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Electron Capture Detector (ECD)


Introduction
The ECD uses a radioactive Beta emitter (electrons) to ionize some of the carrier gas and
produce a current between a biased pair of electrodes. When organic molecules that contain
electronegative functional groups, such as halogens, phosphorous, and nitro groups pass by the
detector, they capture some of the electrons and reduce the current measured between the
electrodes. The ECD is as sensitive as the FID but has a limited dynamic range and finds its
greatest application in analysis of halogenated compounds.

Instrumentation
Schematic of an ECD

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Electron Diffraction
Introduction
Electron diffraction provides similar structural information as neutron diffraction. Electron
beams strongly interact with nuclei and electron diffraction is more useful than X-ray diffraction
for determining proton positions. The strong interaction of electrons with matter results in a low
penetration depth, and electron diffraction is done in a reflection geometry to study surfaces or
thin films or in a transmission mode for films or particles that are sufficiently thin. Electron
beams are easy to manipulate, detect, and focus to small spots to provide high spatial resolution,
which is a major advantage compared to X-ray diffraction. Using the spatial resolution is
referred to as selected-area electron diffraction (SAD).

Instrumentation
Electrons scatter from gases and electron diffraction must be performed under vacuum, usually
in an electron microscope. For sufficiently thin samples, electron diffraction is performed in a
transmission electron microscope (TEM) and the diffraction pattern can be viewed on a phosphor
screen or recorded on film. For more experimental details see the electron microscope document.
Surface diffraction
Electron diffraction can be surface selective by using a grazing incidence geometry or by using
low-energy electrons at normal incidence. These two methods are called reflection high-energy
electron diffraction (RHEED) and low-energy electron diffraction (LEED). Diffraction
experiments can be made with electron energies between these two cases, and these experiments
are called medium-energy electron diffraction (MEED). The energies of the incident electron for
these experiments are given below.

LEED 10 - 500 eV
MEED 500 eV - 10 keV
RHEED 10 - 100 keV

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Index of Electronic Circuit Components


Introduction
This page is an alphabetical list of electronics components with their common circuit symbols.
The headings with links lead to more detailed tutorial documents on those components. The
unlinked headings are of very simple devices that are included only to illustrate their circuit
symbols.

The descriptive documents will often refer to a component as either a passive or an active device.
Passive components, such as resistors and capacitors, are generally two-terminal devices that
have no external power source. Active devices, such as transistors, have more than two terminals
and have are externally powered so that the device output can be amplified compared to an input.

Capacitors
Diodes

Fuses

Note: the SB in the example means "slow blow"

Ground or earth

Note: multiple ground symbols in a circuit imply that they are connected to a common ground.

Lamps
Inductors

Meters

Note: The voltmeter is used in parallel to measure the potential difference between two points
and the ammeter is used in series to measure the current through a point.

Operational Amplifiers (op-amps)

Note: The power supply leads, V+ and V-, are often left out of circuit diagrams.

Oscillators (quartz crystal)

Power Supplies
Battery or dc power source

ac power sources

Resistors

Silicon-controlled rectifier (SCR)

Switches
Transformers

Transistors
bipolar

B = base, C = collector, and E = emitter

JFET
MOSFET
D = drain and S = source

Note: transistor terminals are usually not labeled in circuit diagrams.

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Index of Electronic Circuit Components


Introduction
This page is an alphabetical list of electronics components with their common circuit symbols.
The headings with links lead to more detailed tutorial documents on those components. The
unlinked headings are of very simple devices that are included only to illustrate their circuit
symbols.

The descriptive documents will often refer to a component as either a passive or an active device.
Passive components, such as resistors and capacitors, are generally two-terminal devices that
have no external power source. Active devices, such as transistors, have more than two terminals
and have are externally powered so that the device output can be amplified compared to an input.

Capacitors

Diodes

Fuses

Note: the SB in the example means "slow blow"

Ground or earth
Note: multiple ground symbols in a circuit imply that they are connected to a common ground.

Lamps

Inductors

Meters

Note: The voltmeter is used in parallel to measure the potential difference between two points
and the ammeter is used in series to measure the current through a point.

Operational Amplifiers (op-amps)


Note: The power supply leads, V+ and V-, are often left out of circuit diagrams.

Oscillators (quartz crystal)

Power Supplies
Battery or dc power source

ac power sources

Resistors
Silicon-controlled rectifier (SCR)

Switches

Transformers

Transistors
bipolar

B = base, C = collector, and E = emitter


JFET
MOSFET
D = drain and S = source

Note: transistor terminals are usually not labeled in circuit diagrams.

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Introduction to Detection Electronics


Introduction
An analytical signal usually comes from some type of light detector, ion detector, or sensor. To
be useful this analytical signal must often be converted from a current to a voltage, averaged, or
manipulated, and stored.

Detection Electronics
 Current-to-voltage conversion
 Gated integrator
 Lock-in amplifier
 Oscilloscope
o introduction
o digital oscilloscope
 Pulse counting (photon counting)
 Transient recorder

Related Topics
 Introduction to electronics
 Introduction to computer data acquisition

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Electron Microscopy
Introduction
Electron microscopy is an imaging technique that uses an electron beam to probe a material.
Since the wavelength of an electron is much smaller than the wavelength of visible light,
diffraction effects occur at much smaller physical dimensions. The imaging resolution in electron
microscopy is on the order of 1 nm, which is much better than the µm resolution of light
microscopy. When electrons penetrate a sample, they are diffracted to form a diffraction pattern.
This diffraction pattern can be transformed with a lens to obtain the sample image. Electron
microscopy finds its widest use in materials science and microbiology.

Instrumentation
The use of electron beams requires that the sample be placed in a vacuum chamber for analysis.
An electron beam is produced by applying a high voltage to a hot tungsten filament, and
accelerating the emitted electrons through a high electric field, typically 10-100 keV. The
electron beam is then focused with magnetic field lenses to a typical spot diameter of 1-100 nm
on the sample.

Transmission electron microscopy (TEM)


Transmission electron microscopy (TEM) images the electrons that pass through a sample. Since
electrons interact strongly with matter, electrons are attenuated as they pass through a solid and
require the samples to be prepared in very thin sections, less than 100 nm. Specialized electron
microscopes can use electron energies on the order of a MeV to study samples as thick as 1 µm
or more. Materials samples are or for particles dispersed as a monolayer on a support grid.
Biological samples are embedded in a solid matrix and microtomed. In all cases, the sample is
placed on some type of support grid. Either the diffraction pattern or the image of the sample is
observed on a phosphor screen below the sample, and can be recorded with film.

High resolution electron microscopy (HREM)


High resolution electron microscopy (HREM) is a variation of TEM that uses phase-contrast
microscopy to achieve a resolution of approximately 0.2 nm, which is sufficient to provide
atomic-scale resolution. The phase-contrast method uses the phase difference of multiple
diffracted beams in addition to the intensity of the diffracted beams. The lattice image that is
reconstructed is valid only when the electron beam has a spatial resolution of approximately 0.2
nm and the sample is thin enough that electrons are not scattered multiple times (less than
approximately 10 nm). Under these conditions the reconstructed lattice image represents the true
structure.

Scanning electron microscopy (SEM)


Scanning electron microscopy (SEM) uses the secondary electrons that are ejected from a sample
to image a surface. These images are useful for studying surface morphology or measuring
particle sizes. The electron beam is rastered across the sample by ramping the voltages on x- and
y-deflection plates through which the electron beam passes (the z axis is the electron-beam
direction). A detector above the sample detects the secondary electrons to produce an intensity
map as a function of electron-beam position, which is displayed on a video or computer screen.
Nonconductive samples require an evaporated gold or graphite coating over the sample to
prevent charging effects that would distort the electric fields in the electron microscope.

A recent innovation in scanning electron microscopy is to use several stages of differential


pumping between the electron gun and the sample, which is placed in a vacuum of a few torr.
This method is called environmental scanning electron microscopy (E-SEM) and allows imaging
of samples that would quickly vaporize in a high-vacuum environment.

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Ion Detectors
Channeltron
A channeltron is a horn-shaped continuous dynode structure that is coated on the inside with a
electron emissive material. An ion striking the channeltron creates secondary electrons that have
an avalanche effect to create more secondary electrons and finally a current pulse.
Daly detector
A Daly detector consists of a metal knob that emits secondary electrons when struck by an ion.
The secondary electrons are accelerated onto a scintillator that produces light that is then
detected by a photomultiplier tube.

Electron multiplier tube (EMT)


Electron multiplier tubes are similar in design to photomultiplier tubes. They consist of a series
of biased dynodes that eject secondary electrons when they are struck by an ion. They therefore
multiply the ion current and can be used in analog or digital mode.

Faraday cup
A Faraday cup is a metal cup that is placed in the path of the ion beam. It is attached to an
electrometer, which measures the ion-beam current. Since a Faraday cup can only be used in an
analog mode it is less sensitive than other detectors that are capable of operating in pulse-
counting mode.

Microchannel plate
A microchannel plate (MCP) consists of an array of glass capillaries (10-25 � m inner diameter)
that are coated on the inside with a electron-emissive material. The capillaries are biased at a
high voltage and like the channeltron, an ion that strikes the inside wall one of the capillaries
creates an avalanche of secondary electrons. This cascading effect creates a gain of 103 to 104
and produces a current pulse at the output.
Schematic of a microchannel plate

Microchannel plates (MCP) are also used as an intensifier for low-intensity light detection with
array detectors.

Related topics
 Introduction to mass spectrometry

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Electron Paramagnetic Resonance (EPR,


ESR) Spectroscopy
Introduction
When an atom or molecule with an unpaired electron is placed in a magnetic field, the spin of the
unpaired electron can align either in the same direction or in the opposite direction as the field.
These two electron alignments have different energies and application of a magnetic field to an
unpaired electron lifts the degeneracy of the � 1/2 spins of the electron.

Electron-paramagnetic-resonance (EPR) or electron-spin-resonance (ESR) spectroscopy


measures the absorption of microwave radiation by an unpaired electron when it is placed in a
strong magnetic field.
Species that contain unpaired electrons:

1. Free radicals
2. Odd electron molecules
3. Transition-metal complexes
4. Lanthanide ions
5. Triplet-state molecules

Instrumentation
A klystron tube generates monochromatic microwave radiation (~9500 MHz) in an EPR
instrument. The microwave radiation travels down a waveguide to the sample which is held
between magnets.

Spectra are obtained by measuring the absorption of the microwave radiation while scanning the
magnetic-field strength. EPR spectra are usually displayed in derivative form to improve the
signal-to-noise ratio.

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Electron Spectroscopy
Introduction
Electron spectroscopies analyze the electrons that are ejected from a material for qualitative or
semi-quantitative analysis. In general an excitation source such as X-rays or electrons will eject
an electron from an inner-shell orbital of an atom. Detecting photoelectrons that are ejected by
X-rays is call X-ray photoelectron spectroscopy (XPS) or electron spectroscopy for chemical
analysis (ESCA). Detecting electrons that are ejected from higher orbitals to conserve energy
during electron transitions is called Auger electron spectroscopy (AES). These electron processes
are described below. Ejected electrons can escape only from a depth of approximately 3 nm or
less, making electron spectroscopy most useful to study surfaces of solid materials. Depth
profiling is accomplished by combining an electron spectroscopy with a sputtering source that
removes surface layers.

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Electrophoresis
Introduction
Electrophoresis is a separations technique that is based on the the mobility of ions in an electric
field. Positively charged ions migrate towards a negative electrode and negatively-charged ions
migrate toward a positive electrode.For safety reasons one electrode is usually at ground and the
other is biased positively or negatively. Ions have different migration rates depending on their
total charge, size, and shape, and can therefore be separated.

Instrumentation
An electrode apparatus consists of a high-voltage supply, electrodes, buffer, and a support for the
buffer such as filter paper, cellulose acetate strips, polyacrylamide gel, or a capillary tube. Open
capillary tubes are used for many types of samples and the other supports are usually used for
biological samples such as protein mixtures or DNA fragments. After a separation is completed
the support is stained to visualize the separated components.

Resolution can be greatly improved using isoelectric focusing. In this technique the support gel
maintains a pH gradient. As a protein migrates down the gel, it reaches a pH that is equal to its
isoelectric point. At this pH the protein is netural and no longer migrates, i.e, it is focused into a
sharp band on the gel.

Schematic of zone electrophoresis apparatus


Specific electrophoretic techniques
 disc electrophoresis
 capillary electrophoresis
 gel electrophoresis (SDS-PAGE)

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Emission
Introduction
Atoms, molecules, or solids that are excited to high energy levels can decay to lower levels by
emitting radiation (emission or luminescence). For atoms excited by a high-temperature energy
source this light emission is commonly called atomic or optical emission (see atomic-emission
spectroscopy) and for atoms excited with light it is called atomic fluorescence (see atomic-
fluorescence spectroscopy). For molecules it is called fluorescence if the transition is between
states of the same spin and phosphorescence if the transition occurs between states of different
spin. Separate documents describe molecular fluorescence, which can be done with compact
instruments, and laser-induced fluorescence.

The emission intensity of an emitting substance is linearly proportional to analyte concentration


at low concentrations. Atomic emission and molecular fluorescence are therefore useful for
quantitating emitting species.

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Energy Levels
Introduction
Due to the quantized nature of everything, the possible energy of an electronic orbital, molecular
vibration, or rotation is restricted to a well-defined energy.

Atomic Energy Levels

Molecular Energy Levels

Solid State Band Theory

Related topics
 Electromagnetic Spectrum
 Interaction of Light with Matter
 Spectroscopy

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Reaction Thermodynamics
Introduction
This doucument introduces the thermodynamics of chemical reactions. To start, imagine the
following demonstration: Cold packs contain separate compartments of water and a salt such as
ammonium nitrate. When you mix the salt and water the cold pack gets cold. Such a reaction is
called an endothermic reaction.

NH4NO3 (s) NH4+(aq) + NO3-(aq) Ho = +28.1 kJ/mol

This reaction is spontaneous even though thermal energy is needed to break the ionic bonds of
the crystalline NH4NO3.

Why do endothermic reactions occur?

The driving force for the NH4NO3 reaction is the much greater disorder that is possible for the
NH4+ and NO3- ions in solution compared to these ions arranged in a solid.
We describe the disorder or randomness of a system with the entropy, S, which has units of
kJ/mol·K.

Qualitative examples:

Liquids are more disordered than solids and gases are more disordered than liquids.
At 0oC SH2O(l) > SH2O(s)
At 100oC SH2O(g) > SH2O(l)

As 90 people enter a 180-seat lecture hall, do they take seats beginning in the front row to
completely fill the front half of the room and leaving the back half of the room empty? No, the
probability of that arrangement is very, very small. The more likely arrangement is for the 90
people to more or less distribute themselves randomly in the room. This arrangement is more
probable and we could quantitate this more probable arrangement in terms of entropy.

Spontaneity and Gibbs Free Energy


The entropy must be included to predict if a reaction will be spontaneous. The total change in the
available energy of a system is called the change in the Gibbs free energy, G:

G= H-T S
Where
G is the change in Gibbs free energy (kJ/mol)
H is the change in enthalpy (kJ/mol)
T is absolute temperature in K
S is the change in entropy (kJ/mol K)

The change in enthalpy is the amount of heat or work that is transferred when an reaction occurs.

A reaction is spontaneous if G is negative, that is, the products have a lower Gibbs free energy
than the reactants.

Note that depending on the sign of H and S, the spontaneity of a reaction can be
temperature dependent.

For standard conditions of 1 atm for gases and 1 M for solutes in solution, these energies are
given an "o" superscript. The change in energy for any reaction (at standard conditions) can be
found using tabulated standard energies of formation and standard entropies.
The f subscript for the Hfo and Gfo indicates standard heats of formation. I've used the rexn
subscript to specify that the energy changes are of a reaction. This subscript is usually left off.

From tables of standard enthalpies and free energies we can calculate Ho and Go for this
reaction.
NH4NO3 (s) NH4+(aq) + NO3-(aq)

Hfo (kJ/mol) Gfo (kJ/mol)

NH4NO3 (s) -365.6 -184.0

NH4+(aq) -132.5 -79.3

NO3-(aq) -205.0 -108.7

Ho = -132.5 kJ/mol - 205.0 kJ/mol - (-365.6 kJ/mol)

Ho = +28.1 kJ/mol

Go = -79.3 kJ/mol - 108.7 kJ/mol - (-184 kJ/mol)

Go = -4.0 kJ/mol

Since Go is a negative number this reaction is spontaneous at standard concentrations. (We


also observed that this reaction was spontaneous for the salt concentrations in the cold pack,
which were probably higher than 1 M.)

Activation Energy Diagram


Recall the activation energy diagram that was introduced in the kinetics document. The model is
valid for both exothermic or endothermic reactions.

A diagram for an exothermic reaction:


^
| ________
Energy | / \
| reactants / Ea \
| __________/ __ \
| \
| \
| G \
| \ products
| __ \_________
|
|

A diagram for an endothermic reaction:

^
| ________
Energy | / \
| / \
| / \
| / \ products
| / Ea \____________
| /
| reactants / G
| ___________/ ___ ___
|
|

Ea is the activation energy and G is the chagne in Gibbs free energy (in kJ/mol).

Don't Forget the Really Big Concepts in Chemistry


Kinetics describes how quickly or slowly a reaction occurs.

Thermodynamics describes the changes in the form of energy when a reaction occurs, for
example, converting chemical energy to heat.

Equilibrium describes reactions in which the reactants and products coexist.

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X-ray Photoelectron Spectroscopy (XPS,
ESCA)
Introduction
X-ray photoelectron spectroscopy (XPS, also called electron Energy-level diagram for XPS
spectroscopy for chemical analysis, ESCA) is a electron
spectroscopic method that uses X-rays to eject electrons
from inner-shell orbitals. The kinetic energy, Ek, of these
photoelectrons is determined by the energy of the X-ray
radiation, h , and the electron binding energy, Eb, as given
by:

Ek = h - Eb

The experimentally measured energies of the photoelectrons


are given by:

Ek = h - Eb - Ew

where Ew is the work function of the spectrometer.

The electron binding energies are dependent on the chemical environment of the atom, making
XPS useful to identify the oxidation state and ligands of an atom.

Instrumentation
XPS instruments consist of an X-ray source, an energy analyzer for the photoelectrons, and an
electron detector. The analysis and detection of photoelectrons requires that the sample be placed
in a high-vacuum chamber. Since the photoelectron energy depends on X-ray energy, the
excitation source must be monochromatic. The energy of the photoelectrons is analyzed by an
electrostatic analyzer, and the photoelectrons are detected by an electron multiplier tube or a
multichannel detector such as a microchannel plate.

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Introduction to Equilibrium
Introduction
Equilibrium is the condition at which a system is not changing. State variables such as
temperature and pressure are constant, the number of phases is not changing, and the
concentrations of the components of the system are not changing. Reactions are still occurring on
the microscopic scale, but the macroscopic concentrations are not changing.

When we say a system is at equilibrium we always mean that it is in a thermodynamic


equilibrium. A system might be kinetically stable or metastable, but not at equilibrium. A
balloon containing a mixture of H2 and O2 at room temperature is not in equilibrium. However, it
does not explode without a spark. Similarly, equilibrium and a "steady state" are not necessarily
the same thing. An open system in which reactants are entering and products are leaving a
reactor can be in a steady state but not at equilibrium.

Equilibrium is described quantitatively by the equilibrium constant. The related reaction quotient
provides a quantitative measure of how far a system is from equilibrium.

Specific Chemical Equilibria


A chemical specie will always exist in equilibrium with other forms of itself. The other forms
may exist in undetectable amounts but they are always present. These other forms arise due to
the natural disorder of nature that we call entropy (it's impossible to be perfect). As an example,
pure water consists of the molecular compound and dissociated ions that exist together in
equilibrium:

H2O(l) H+(aq) + OH-(aq)

The (l) subscript refers to the liquid state, and the (aq) subscript refers to ions in aqueous
solution.

More details are available for the following classifications of chemical equilibria:

 Acids and Bases - Kw, Ka, and Kb.


 Precipitation - Solubility of insoluble salts, Ksp.
 Complexation - Formation of complexes between metal ions and ligands, Kf.

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Equilibrium Practice
Problems
Table of Contents

User Notes CHP Home

I. II. III. VI. V. VI. VII.


Review Introduction and Gas-Phase Weak Advanced Buffers Precipitation
General Solution Equilibria Acids Acid/Base
and
Bases

I. Background Review
Review the following background material before beginning the equilibria problems. You might
also want to try the pretest on basic math and chemical concepts.

I-1. Pretest
I-2. Problem Solving
I-3. Math Review
I-4. Chemistry Units
I-5. Reactions
I-6. Stoichiometry (balancing reactions)
I-7. Spectator Ions

II. General Solution to Equilibria Problems


II-1. Introduction
II-2. Equilibrium Constant
II-3. Le Chatelier's Principle
II-4. Reaction Quotient
II-5. General Solution

III. Gas-Phase Equilibria


III-1. Introduction
III-2. Sample Gas-Phase Problem
III-3. List of Gas-Phase Problems
III-4. Simple Gas-Phase Problems
III-5. Advanced Gas-Phase Problems

IV. Weak Acids and Weak Bases


IV-1. Introduction
IV-2. Sample Problems
IV-3. List of Weak Acid and Weak Base Problems
IV-4. Weak Acid Problems
IV-5. Weak Base Problems

V. Advanced Weak Acid and Weak Base Problems


V-1. Introduction to Acidic and Basic Salts
V-2. Acidic and Basic Salt Sample Problem
V-3. List of Acidic and Basic Salt Problems
V-4. Acidic and Basic Salt Problems

VI. Buffers
VI-1. Buffers Introduction and Sample Problem
VI-2. Polyprotic Acids Introduction and Sample Problem
VI-3. List of Buffer and Polyprotic Acid Problems
VI-4. Buffer Problems
VI-5. Polyprotic Acid Problems

VII. Precipitation Equilibria


VII-1. Introduction
VII-2. Sample Precipitation Problem
VII-3. List of Precipitation Problems
VII-4. Simple Precipitation Problems
VII-5. Advanced Precipitation Problems

Equilibrium Practice Problems

CHP Home Table of Contents


Jump to the top of this page.

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Equilibrium Constant, K
Introduction
The equilibrium between reactants and products is described by an equilibrium constant. For the
balanced reaction:
aA + bB cC + dD
The equilibrium constant, Keq is defined as:

[C]c [D]d
Keq = ---------
[A]a [B]b
where the [] brackets indicate the concentration of the chemical species.

Rules for Writing K Expressions


1. Products are always in the numerator.
2. Reactants are always in the denominator.
3. Express gas concentrations as partial pressure, P, and dissolved species in molar
concentration, [].
4. The partial pressures or concentrations are raised to the power of the stoichiometric
coefficient for the balanced reaction.
5. Leave out pure solids or liquids and any solvent. Only variables will be in a K
expression: partial pressure of gases and concentrations of solutes in solution.

Example:

Zn (s) + 2 H+(aq) Zn2+(aq) + H2 (g)

PH2 [Zn2+]
K = -----------
[H+]2

Specific Equilibrium Constants


The equilbrium constant has specific names for several classes of reactions:
1. Gas-phase reactions that use units of partial pressure: Kp
2. Dissociation of water: dissociation constant of water, Kw
3. Dissociation of acids: acid dissociation constant, Ka
4. Reaction of bases with water: base hydrolysis constant, Kb
5. Solubility of precipitates: solubility product, Ksp
6. Formation of complexes: formation constant, Kf

Each of these classifications of reactions will have a convention for how to write the direction of
the reaction. The different conventions are illustrated in the introduction to reactions document.

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Error
Random Error
Random error is the irreproducibility in making replicate measurements and affects the precision
of a result. The distribution of random errors follows a Gaussian-shape "bell" curve. The
precision is described by statistical quantities such as the standard deviation.

Systematic Error
Systematic errors are errors that produce a result that differs from the true value by a fixed
amount. These errors result from biases introduced by instrumental method, or human factors.

An example of an instrumental bias is an incorrectly calibrated pH meter that shows pH values


0.5 units lower than the true value. An example of a method error would be partial loss of a
volatile analyte during the ashing step in graphite furnace atomic absorption (AA) spectroscopy.
An example of human bias is a student who records titration endpoints beyond the true endpoint
due to color blindness.

Systematic errors can be identified and corrected by analyzing standards that closely match the
real sample.

Related topics:
 data handling

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Propagation of Error
Introduction
The error, f, in a final result, F, derives from the error in each measurement or number (x, y,...)
used to get that result. The error in a result, F� f, for F = f(x,y,...) is found from:

f = (dF/dx) ex + (dF/dy) ey + ...

where dF/dx is the partial derivative of F with respect to x, and ex is the uncertainty in x.

Related topics:
 data handling

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Extended X-ray Absorption Fine Structure


(EXAFS)
Introduction to X-ray Absorption
An atom absorbs an X-ray when the photon energy is sufficient to eject a photoelectron (see the
XPS document for an energy level diagram). Below this threshold energy there is no absorption.
Photons with energies greater than the threshold energy to produce a photoelectron are absorbed
because the excess energy is conserved by transferring it to kinetic energy of the photoelectron.
However, the probability of the absorption occuring decreases as the photon energy increases
above the threshold.

Use of X-ray absorption as an analytical method is fairly uncommon because other techniques
such as X-ray fluorescence are more sensitive. The absorption of X-rays by a certain element is
often used in analytical instrumentation as a filter to block some X-ray wavelengths. For
example, the absorption edge of Zr will block KB and most of the continuum radiation of X-rays
from a Mo target.

Extended X-ray Absorption Fine Structure (EXAFS)


Extended X-ray Absorption Fine Structure (EXAFS) occurs due to interference effects as
photoelectrons leave the surface of a material. The interference depends on the interatomic
distance between the atom that ejected the photoelectron and the nearest neighbor atom, and to
lesser extents the next nearest neighbor and other atoms. EXAFS therefore provides a means to
determine the structure of the atoms on the surface of a material. The fine structure appears as a
modulation on the absorption edge, and requires sophisticated modeling to extract the structural
information about the sample surface. The most common source for EXAFS is synchrotron
radiation, which provides an intense and tunable source of X-rays.

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Extraction
Introduction
Extractions use two immiscible phases to separate a solute from one phase into the other. The
distribution of a solute between two phases is an equilibrium condition described by partition
theory. Boiling tea leaves in water extracts the tannins, theobromine, and caffeine (the good
stuff) out of the leaves and into the water. More typical lab extractions are of organic compounds
out of an aqueous phase and into an organic phase.
Illustration of an extraction in a separatory funnel

Analytical Extractions
Elemental analysis generally requires fairly simple (not necessarily easy) sample preparation.
Solids are usually dissolved or digested in caustic solution and liquids are sometimes extracted to
separate the analyte from interferences.

Organic analysis is often much more complicated. Real-world samples can be very complicated
matrices that require careful extraction procedures to obtain the analyte(s) in a form that can be
analyzed.

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Fabry-Perot Interferometer
Introduction
The Fabry-Perot interferometer is commonly used as a narrow-bandpass filter or as an
instrument to measure spectral linewidths.

Fabry-Perot interferometer (etalon)


Fabry-Perot interferometers that cannot be scanned are called etalons.

Schematic of a Fabry-Perot etalon

Transmission through a Fabry-Perot interferometer as a function of wavelength

Related Topics
 Other Interferometers
 Optics
 Optical Materials

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Field-Effect Transistors (FET)


Introduction
The FET behaves like a bipolar transistor with the important difference that the gate has a very
high input impedance and therefore draws no current. There are two main varieties, JFETs
(junction FETs) and MOSFETs (metal-oxide-semiconductor FETs).

Circuit symbol:

http://www.files.chem.vt.edu/chem-ed/electronics/devices/fet.html, updated Top of


01/24/2012 11:30:38 Page

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Filters
Introduction
Filters separate different parts of the electromagnetic spectrum by absorbing or reflecting certain
wavelengths and transmitting other wavelengths.

Color Filters
Color filters are glass substrates containing absorbing species that absorb certain wavelengths. A
typical example is a cut-on color filter, which blocks short wavelength light such as an excitation
source, and transmits longer wavelength light such as fluorescence that reaches a detector.

Interference Filters
Interference filters are made of multiple dielectric thin films on a substrate. They use interference
to selectively transmit or reflect a certain range of wavelengths. A typical example is a bandpass
interference filter that transmits a narrow range of wavelengths, and can isolate a single emission
line from a discharge lamp.

Related Topics
 Optics
 Optical Materials

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Flame-Ionization Detector (FID)


Introduction
An FID consists of a hydrogen/air flame and a collector plate. The effluent from the GC column
passes through the flame, which breaks down organic molecules and produces ions. The ions are
collected on a biased electrode and produce an electrical signal. The FID is extremely sensitive
with a large dynamic range. Its only disadvantage is that it destroys the sample.
Schematic of FID

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Flame Photometric GC Detector (FPD)


Introduction
The reason to use more than one kind of detector for gas chromatography is to achieve selective
and/or highly sensitive detection of specific compounds encountered in particular
chromatographic analyses. The determination of sulfur or phosphorus containing compounds is
the job of the flame photometric detector (FPD). This device uses the chemiluminescent
reactions of these compounds in a hydrogen/air flame as a source of analytical information that is
relatively specific for substances containing these two kinds of atoms. The emitting species for
sulfur compounds is excited S2. The lambda max for emission of excited S2 is approximately 394
nm. The emitter for phosphorus compounds in the flame is excited HPO (lambda max = doublet
510-526 nm). In order to selectively detect one or the other family of compounds as it elutes
from the GC column, an interference filter is used between the flame and the
Instrumentation
In addition to the instrumental requirements for 1) a combustion chamber to house the flame, 2)
gas lines for hydrogen (fuel) and air (oxidant), and 3) an exhaust chimney to remove combustion
products, the final component necessary for this instrument is a thermal (bandpass) filter to
isolate only the visible and UV radiation emitted by the flame. Without this the large amounts of
infrared radiation emitted by the flame's combustion reaction would heat up the PMT and
increase its background signal. The PMT is also physically insulated from the combustion
chamber by using poorly (thermally) conducting metals to attach the PMT housing, filters, etc.

The physical arrangement of these components is as follows: flame (combustion) chamber with
exhaust, permenant thermal filter (two IR filters in some commercial designs), a removable
phosphorus or sulfur selective filter, and finally the PMT.

Schematic of a gas chromatographic flame photometric detector

These notes were written by Dr. Thomas G. Chasteen at Sam Houston State University,
Huntsville, Texas.
http://www.files.chem.vt.edu/chem-ed/sep/gc/detector/fpd.html, updated Top of
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Emission
Introduction
Atoms, molecules, or solids that are excited to high energy levels can decay to lower levels by
emitting radiation (emission or luminescence). For atoms excited by a high-temperature energy
source this light emission is commonly called atomic or optical emission (see atomic-emission
spectroscopy) and for atoms excited with light it is called atomic fluorescence (see atomic-
fluorescence spectroscopy). For molecules it is called fluorescence if the transition is between
states of the same spin and phosphorescence if the transition occurs between states of different
spin. Separate documents describe molecular fluorescence, which can be done with compact
instruments, and laser-induced fluorescence.

The emission intensity of an emitting substance is linearly proportional to analyte concentration


at low concentrations. Atomic emission and molecular fluorescence are therefore useful for
quantitating emitting species.

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Molecular Fluorescence Spectroscopy


Introduction
Molecular fluorescence is the optical emission from molecules that have been excited to higher
energy levels by absorption of electromagnetic radiation. The main advantage of fluorescence
detection compared to absorption measurements is the greater sensitivity achievable because the
fluorescence signal has in principle a zero background. Analytical applications include
quantitative measurements of molecules in solution and fluorescence detection in liquid
chromatography. The theory of quantitative fluorescence measurements is given in a separate
document.
Transitions between molecular electronic energy levels:

Instrumentation
A typical fluorimeter contains an excitation source, sample cell, fluorescence detector. Molecules
in solution are usually excited by uv light and the excitation source is usually a deuterium or
xenon lamp. Broad-band excitation light from a lamp passes through a monochromator, which
passes only a selected wavelength. The fluorescence is dispersed by another monochromator and
detected by a photomultiplier tube. Scanning the excitation monochromator gives the excitation
spectrum and scanning the fluorescence monochromator gives the fluorescence spectrum. Simple
instruments sometimes use only a bandpass filter to select the excitation wavelength.
Fluorimeter schematic

Related Topics
Because of the differences in the nature of the energy-level structure and dynamics, discussion of
atomic-fluorescence spectroscopy (AFS) and high-resolution laser-induced molecular
fluorescence are in separate documents.

http://www.files.chem.vt.edu/chem-ed/spec/molec/mol-fluo.html, updated Top of


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Laser-Induced Fluorescence (LIF)


Introduction
Laser-induced fluorescence (LIF) is the optical emission from molecules that have been excited
to higher energy levels by absorption of electromagnetic radiation. The main advantage of
fluorescence detection compared to absorption measurements is the greater sensitivity achievable
because the fluorescence signal has a very low background. For molecules that can be resonant
excitated, LIF provides selective excitation of the analyte to avoid interferences. LIF is useful to
study the electronic structure of molecules and to make quantitative measurements of analyte
concentrations. Analytical applications include monitoring gas-phase concentrations in the
atmosphere, flames, and plasmas; and remote sensing using light detection and ranging
(LIDAR). Because of the differences in the nature of the energy-level structure between atoms
and molecules, the discussion on atomic fluorescence spectroscopy is in a separate document.
Instrumentation
The excitation source for molecular LIF is typically a tunable dye laser in the visible spectral
region. Studies in the near-ultraviolet and near-infrared are becoming more common as near-
infrared lasers and frequency-doubling methods improve. High-resolution studies require cooling
of the molecules to remove spectral congestion and to reduce the Doppler width of the
transitions. A separate document on high-resolution spectroscopy describes cooling methods
such as molecular beams, free-jet expansions, and cryogenic glass or crystalline matrices.

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Quantitative Fluorimetry
Introduction
Light emission from atoms or molecules can be used to quantitate the amount of the emitting
substance in a sample. The relationship between fluorescence intensity and analyte concentration
is:
F = k * QE * Po * (1-10[- *b*c])
where F is the measured fluorescence intensity, k is a geometric instrumental factor, QE is the
quantum efficiency (photons emitted/photons absorbed), Po is the radiant power of the excitation
source, is the wavelength-dependent molar absorptivity coefficient, b is the path length, and c
is the analyte concentration ( , b, and c are the same as used in the Beer-Lambert law).

Expanding the above equation in a series and dropping higher terms gives:
F = k * QE * Po * (2.303 * * b * c)
This relationship is valid at low concentrations (<10-5 M) and shows that fluorescence intensity
is linearly proportional to analyte concentration.

Determining unknown concentrations from the amount of fluorescence that a sample emits
requires calibration of a fluorimeter with a standard (to determine K and QE) or by using a
working curve.

Limitations
Many of the limitations of the Beer-Lambert law also affect quantitative fluorimetry.
Fluorescence measurements are also susceptible to inner-filter effects. These effects include
excessive absorption of the excitation radiation (pre-filter effect) and self-absorption of atomic
resonance fluorescence (post-filter effect).

Specific fluorescence techniques


 Atomic fluorescence spectroscopy (AFS)
 Molecular laser-induced fluorescence (LIF)

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Fourier-Transform (FT)
Introduction
The Fourier theorem states that any waveform can be duplicated by the superposition of a series
of sine and cosine waves. As an example, the following Fourier expansion of sine waves
provides an approximation of a square wave.

The three curves in the plot show the first one term (black line), four terms (blue line), and
sixteen terms (red line) in the Fourier expansion. As more terms are added the superposition of
sine waves better matches a square wave.
The Fourier Transform uses the above concept to convert between two different descriptions of a
physical system.

In these equations is angular frequency (2 x frequency), t is time, and:

The F( ) function gives the frequencies at which the signal is non-zero and the f(t) function
gives the times at which the signal is non-zero. Both of these functions are suitable descriptions
of a waveform or physical system.
Given a function in time, f(t), we can transform it to an equivalent fuction in frequency, F( ).
We can look at the second expression in detail to understand what is happening.

To do the transform we multiply f(t) times [cos( t)+i sin( t)]. We do this at all times between
and - .

DFT and FFT


Experimental data usually consists of discrete data points rather than a continuous function as
used in the equations above. The Discrete Fourier-Transform (DFT) is an algorithm for doing the
transform with discrete data. The DFT is an order N2 calculation, meaning that the number of
multiplications is equal to the square of the number of data points. This algorithm has been
supplanted by Fast Fourier-Transform (FFT) algorithms, which reduce redundancies and take
much less computer time. The order of this calculation is NlogN.

A key experimental parameter is the sampling frequency, which must be at least twice as large as
the highest frequency component that is present in the data. This sampling rate is called the
Nyquist critical frequency. Sampling at less than the Nyquist frequency results in aliasing of the
result. Aliasing can be prevented by filtering out all frequencies above the Nyquist frequency so
that they do not create artifacts in the transformed spectrum.

The Fourier-Transform in Analytical Instrumentation


Fast Fourier-Transform (FFT) algorithms are used in NMR, infrared, Raman, and mass
spectrometry instrumentation. The advantages are:

 multiplex (or Fellgett) advantage


 throughput (or Jaquinot) advantage
 rapid signal averaging of data to greatly improve the signal-to-noise ratio of the data

The multiplex advantage arises from recording all signal frequencies simultaneously. The
throughput advantage arises because no physical slit is necessary to obtain resolution in the
resulting spectra.

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Fourier-Transform Nuclear Magnetic


Resonance (FT-NMR) Spectroscopy
Introduction
Fourier-transform NMR spectrometers use a pulse of radiofrequency (RF) radiation to cause
nuclei in a magnetic field to flip into the higher-energy alignment. Due to the Heisenberg
uncertainty principle, the frequency width of the RF pulse (typically 1-10 � s) is wide enough to
simultaneously excite nuclei in all local environments. All of the nuclei will re-emit RF radiation
at their respective resonance frequencies, creating an interference pattern in the resulting RF
emission versus time, known as a free-induction decay (FID). The frequencies are extracted from
the FID by a Fourier transform of the time-based data.

Instrumentation
An FT-NMR spectrometer consists of a control console, magnet, and a coil of wire that serves as
the antenna for transmitting and receiving the RF radiation. (Only one coil is necessary because
signal reception does not begin until after the end of the excitation pulse.) Because the FID
results from the emission due to nuclei in all environments, each pulse contains an interference
pattern from which the complete spectrum can be obtained. Because of this multiplex (or
Fellgett) advantage, repetitive signals can be summed and averaged to greatly improve the
signal-to-noise ratio of the resulting FID.

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Infrared Absorption Spectrometers


Introduction
This document describes dispersive and Fourier-transform spectrometers that are used in infrared
absorption spectroscopy. Common light sources are tungsten lamps, Nernst glowers, or
glowbars. IR detectors consist of a semiconductor such as PbS or liquid-nitrogen-cooled
HgCdTe (also called MCT).

Dispersive infrared spectrometer


Dispersive IR spectrometers use a diffraction grating in a monochromator to disperse the
different wavelengths of light. Dispersive IR spectrometers have largely been replaced with
FTIR instruments. They find some use in specific applications, such as monitoring a single IR
wavelength to measure the kinetics of a fast reaction.

Schematic of a dispersive IR absorption spectrometer

Fourier-transform infrared (FTIR) spectrometer


Most modern IR absorption instruments use Fourier-transform techniques with a Michelson
interferometer. To obtain an IR absorption spectrum, one mirror of the interferometer moves to
generate interference in the radiation reaching the detector. Since all wavelengths are passing
through the interferometer, the interferogram is a complex pattern. The absorption spectrum as a
function of wavenumber (cm-1) is obtained from the Fourier transform of the interferogram,
which is a function of mirror movement (cm). This design does not have the reference cell of a
dispersive instrument, so a reference spectrum is recorded and stored in memory to subtract from
the sample spectrum.
Picture of an FTIR absorption spectrometer

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Fourier-Transform Mass Spectrometry


Introduction
Fourier-transform mass spectrometry takes advantage of ion-cyclotron resonance to select and
detect ions.

Ions in a magnetic field will move in a circular path of radius:

r = mv/eB

and frequency:

f = eB/ m

Ions moving at their cyclotron frequency can absorb RF energy at this same frequency. A pulse
of RF excites the ions in the magnetic field. The ions re-emit the radiation, which is picked up by
the reciever plates. The decay produces a free-indcution decay signal that can be Fourier
transformed to produce the emitted frequencies, and therefore the masses of the ions present.

Instrumentation
Schematic of a FT-MS

FTMS can provide very high resolution, 106, which its main advantage compared to other mass
spectrometers.

Related topics:
 Mass spectrometry (Intro)
 Ionization methods
 Ion detectors

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Emission
Introduction
Atoms, molecules, or solids that are excited to high energy levels can decay to lower levels by
emitting radiation (emission or luminescence). For atoms excited by a high-temperature energy
source this light emission is commonly called atomic or optical emission (see atomic-emission
spectroscopy) and for atoms excited with light it is called atomic fluorescence (see atomic-
fluorescence spectroscopy). For molecules it is called fluorescence if the transition is between
states of the same spin and phosphorescence if the transition occurs between states of different
spin. Separate documents describe molecular fluorescence, which can be done with compact
instruments, and laser-induced fluorescence.

The emission intensity of an emitting substance is linearly proportional to analyte concentration


at low concentrations. Atomic emission and molecular fluorescence are therefore useful for
quantitating emitting species.

http://www.files.chem.vt.edu/chem-ed/spec/emission.html, updated 01/24/2012 Top of Page


11:39:09
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Atomic-Fluorescence Spectroscopy (AFS)


Introduction
Atomic fluorescence is the optical emission from gas-phase atoms that have been excited to
higher energy levels by absorption of electromagnetic radiation. The main advantage of
fluorescence detection compared to absorption measurements is the greater sensitivity achievable
because the fluorescence signal has a very low background. The resonant excitation provides
selective excitation of the analyte to avoid interferences. AFS is useful to study the electronic
structure of atoms and to make quantitative measurements. Analytical applications include
flames and plasmas diagnostics, and enhanced sensitivity in atomic analysis. Because of the
differences in the nature of the energy-level structure between atoms and molecules, discussion
of laser-induced fluorescence (LIF) from molecules is found in a separate document.

Instrumentation
Analysis of solutions or solids requires that the analyte atoms be desolvated, vaporized, and
atomized at a relatively low temperature in a heat pipe, flame, or graphite furnace. A hollow-
cathode lamp or laser provides the resonant excitation to promote the atoms to higher energy
levels. The atomic fluorescence is dispersed and detected by monochromators and
photomultiplier tubes, similar to atomic-emission spectroscopy instrumentation.

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Molecular Fluorescence Spectroscopy
Introduction
Molecular fluorescence is the optical emission from molecules that have been excited to higher
energy levels by absorption of electromagnetic radiation. The main advantage of fluorescence
detection compared to absorption measurements is the greater sensitivity achievable because the
fluorescence signal has in principle a zero background. Analytical applications include
quantitative measurements of molecules in solution and fluorescence detection in liquid
chromatography. The theory of quantitative fluorescence measurements is given in a separate
document.

Transitions between molecular electronic energy levels:

Instrumentation
A typical fluorimeter contains an excitation source, sample cell, fluorescence detector. Molecules
in solution are usually excited by uv light and the excitation source is usually a deuterium or
xenon lamp. Broad-band excitation light from a lamp passes through a monochromator, which
passes only a selected wavelength. The fluorescence is dispersed by another monochromator and
detected by a photomultiplier tube. Scanning the excitation monochromator gives the excitation
spectrum and scanning the fluorescence monochromator gives the fluorescence spectrum. Simple
instruments sometimes use only a bandpass filter to select the excitation wavelength.

Fluorimeter schematic

Related Topics
Because of the differences in the nature of the energy-level structure and dynamics, discussion of
atomic-fluorescence spectroscopy (AFS) and high-resolution laser-induced molecular
fluorescence are in separate documents.

http://www.files.chem.vt.edu/chem-ed/spec/molec/mol-fluo.html, updated Top of


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Complexation Equilibria
Introduction
Many metal ions form complexes with ligands that can donate electrons to empty orbitals on the
metal. The equilibrium between the metal ion and the ligands is always written with the
formation of the complex being the forward direction. For example:

Co2+ (aq) + 6 NH3 (aq) Co(NH3)62+(aq)

The equilibrium constant expression for a complex is written following the same rules as for any
other equilibrium. The equilibrium constant is called the formation constant, Kf. The Kf
expression for the above equilibrium is:
[Co(NH3)62+]
Kf = ------------
[Co2+][NH3]6
Kf Values for Some Complexes
Formula Name Ksp
AgCl2- dichlorosilver(I) 1.8x105
Ag(CN)2- dicyanosilver(I) 2x1020
Ag(NH3)2+ diamminesilver(I) 1.7x107
Co(NH3)62+ hexaamminecobalt(II) 1x105
Co(NH3)63+ hexaamminecobalt(III) 1x1023
Co(NH3)5Cl2+ pentaamminechlorocobalt(III) 2x1028

http://www.files.chem.vt.edu/chem-ed/equilibr/complexation.html, updated Top of


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X-ray and Gamma-Ray Detectors


Introduction
X-rays and gamma-rays are high-energy electromagnetic waves with wavelengths less than 1
nm. X-rays usually originate from inner-electron transitions, and gamma-rays (which are of
higher energy than X-rays) originate from nuclear decay processes. X-ray detectors are found in
X-ray spectroscopy instruments and in X-ray diffractometers. Detection of gamma rays is
necessary for characterization of radioactive samples and in elemental analysis by neutron
activation analysis (NAA).

There are three main designs for X-ray and gamma-ray detectors: gas-filled detectors,
scintillation counters, and semiconductor detectors. (These detectors can also be used to detect
and quantify charged particles such as alpha and beta particles.) In all of these designs, an
incoming X-ray or gamma-ray collides with atoms in the detector material to produce a
photoelectrons. The photoelectrons collide within the detector to create more electrons. The
number of electrons depends on the initial energy of the incident X-ray or gamma-ray. The
output of the detector can therefore be analyzed based on pulse height to obtain a spectrum of the
incident radiation.

Gas-Filled Detectors
Gas-filled detectors include proportional counters and Geiger counters. They consist of a metal
container filled with a gas such as Ar, a window that can transmit X-rays and gamma-rays, such
as Be or mylar, and a center wire that serves as an anode. A high voltage is maintained between
the metal container and the anode. When high-energy rays or particles that pass into the detector
collide with a gas atom, they ionize the atom to create a photoelectron. The photoelectron has a
high energy and ionizes other gas atoms with which it collides. The result is a cascade of
electrons that are accelerated and collected by the anode and detected as an electrical pulse.

Scintillators
A scintillator is a material that emits light when it absorbs radiation. The light pulse is then
converted to an electrical pulse by a photomultiplier tube. Common scintillators are thallium-
doped NaI, some plastics, anthracene and other organic solids, and liquid scintillation
"cocktails," which are mixed with the sample and are often used in biochemical applications.

Semiconductor Detectors
Semiconductors also produce photoelectrons when high-energy rays or particles strike the
detector material. The most common X-ray and gamma-ray detectors use lithium-drifted silicon
Si(Li) or lithium-drifted germanium Ge(Li). In these detectors, Li is incorporated into the
semiconductor lattice by annealing the semiconductor with Li at a high temperature (~500O). A
voltage of approximately 1000 V is placed across the semiconductor material with two
electrodes, and the electron cascade produced by a photoelectron is detected as an electrical
pulse at the anode.

In addition to being more robust than gas-filled or scintillator detectors, these semiconductor
detectors also provide a much higher resolution. Their only disadvantage is the need for cooling,
usually with liquid nitrogen, to decrease the dark noise of the detector and current-to-voltage
preamplifier.

Related Topics
 Optics
 Optical Materials
 Other radiation detectors

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Gas Chromatography (GC)


Introduction
Gas chromatography is a chromatographic technique that can be used to separate organic
compounds that are volatile. A gas chromatograph consists of a flowing mobile phase, an
injection port, a separation column containing the stationary phase, a detector, and a data
recording system. The organic compounds are separated due to differences in their partitioning
behavior between the mobile gas phase and the stationary phase in the column.

Instrumentation
Mobile phases are generally inert gases such as helium, argon, or nitrogen. The injection port
consists of a rubber septum through which a syringe needle is inserted to inject the sample. The
injection port is maintained at a higher temperature than the boiling point of the least volatile
component in the sample mixture. Since the partitioning behavior is dependant on temperature,
the separation column is usually contained in a thermostat-controlled oven. Separating
components with a wide range of boiling points is accomplished by starting at a low oven
temperature and increasing the temperature over time to elute the high-boiling point components.
Most columns contain a liquid stationary phase on a solid support. Separation of low-molecular
weight gases is accomplished with solid adsorbents. Separate documents describe some specific
GC Columns and GC Detectors.

Schematic of a gas chromatograph

Pictures of some gas chromatographs

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Gas Chromatography (GC)


Introduction
Gas chromatography is a chromatographic technique that can be used to separate organic
compounds that are volatile. A gas chromatograph consists of a flowing mobile phase, an
injection port, a separation column containing the stationary phase, a detector, and a data
recording system. The organic compounds are separated due to differences in their partitioning
behavior between the mobile gas phase and the stationary phase in the column.

Instrumentation
Mobile phases are generally inert gases such as helium, argon, or nitrogen. The injection port
consists of a rubber septum through which a syringe needle is inserted to inject the sample. The
injection port is maintained at a higher temperature than the boiling point of the least volatile
component in the sample mixture. Since the partitioning behavior is dependant on temperature,
the separation column is usually contained in a thermostat-controlled oven. Separating
components with a wide range of boiling points is accomplished by starting at a low oven
temperature and increasing the temperature over time to elute the high-boiling point components.
Most columns contain a liquid stationary phase on a solid support. Separation of low-molecular
weight gases is accomplished with solid adsorbents. Separate documents describe some specific
GC Columns and GC Detectors.

Schematic of a gas chromatograph

Pictures of some gas chromatographs

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Gas Chromatography Columns
Columns
Gas chromatography columns are of two designs: packed or capillary. Packed columns are
typically a glass or stainless steel coil (typically 1-5 m total length and 5 mm inner diameter) that
is filled with the stationary phase, or a packing coated with the stationary phase. Capillary
columns are a thin fused-silica (purified silicate glass) capillary (typically 10-100 m in length
and 250 � m inner diameter) that has the stationary phase coated on the inner surface. Capillary
columns provide much higher separation efficiency than packed columns but are more easily
overloaded by too much sample.

Picture of a packed GC column, Picture of capillary GC column

Stationary Phases
The most common stationary phases in gas-chromatography columns are polysiloxanes, which
contain various substituent groups to change the polarity of the phase. The nonpolar end of the
spectrum is polydimethyl siloxane, which can be made more polar by increasing the percentage
of phenyl groups on the polymer. For very polar analytes, polyethylene glycol (a.k.a. carbowax)
is commonly used as the stationary phase. After the polymer coats the column wall or packing
material, it is often cross-linked to increase the thermal stability of the stationary phase and
prevent it from gradually bleeding out of the column.

Small gaseous species can be separated by gas-solid chromatography. Gas-solid chromatography


uses packed columns containing high-surface-area inorganic or polymer packing. The gaseous
species are separated by their size, and retention due to adsorption on the packing material.

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Gas Chromatography (GC) Detectors


Introduction
After the components of a mixture are separated using gas chromatography, they must be
detected as they exit the GC column. The links listed below provide the details of some specific
GC detectors. The thermal-conductivity (TCD) and flame-ionization (FID) detectors are the two
most common detectors on commercial gas chromatographs. The requirements of a GC detector
depends on the separation application. For example, one analysis might require a detector that is
selective for chlorine-containing molecules, another analysis might require a detector that is non-
destructive so that the analyte can be recovered for further spectroscopic analysis.

Specific GC detectors
Atomic-emmision detector (AED)

Chemiluminescence detector

Electron-capture detector (ECD)


The ECD is as sensitive as the FID but has a limited dynamic range and finds its greatest
application in analysis organic molecules that contain electronegative functional groups,
such as halogens, phosphorous, and nitro groups.
Flame-ionization detector (FID)
The FID is extremely sensitive with a large dynamic range, its only disadvantage is that it
destroys the sample.
Flame-photometric detector (FPD)

Mass spectrometer (MS)


Mass spectrometers provide structural information to identify the analyte in a
chromatographic peak.
Nitrogen-phosphorus detector (NPD)
A detector similar in design to an FID but with selectivity for compounds containing
nitrogen and phosphorus.
Photoionization detector (PID)

Thermal conductivity detector (TCD)


The TCD is not as sensitive as other dectectors but it is non-specific and non-destructive.

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Gated Integrator
Introduction
A gated integrator (also called a boxcar integrator or averager) integrates an analytical signal
over a fixed time window. In pulsed experiments the integrator gate is synchronized with the
analytical signal by a trigger. This method increases the signal-to-noise ratio by recording the
voltage only when the signal is present and ignoring time periods when there is no signal and
only noise. The following plot shows a time dependent signal. The shaded area covers 90% of
the area under the curve. Integrating the signal only during this time period gets most of the
signal and avoids noise at the beginning of the experiment and after the signal has decayed to
zero. (Note that this simulation does not show the noise that would be typical of a real transient
signal.)

Gated integration of a transient signal

Related Topics
 Index of detection electronics
 Introduction to electronics
 Introduction to data acquisition

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Normal Error Curve
Introduction
Random fluctuations result in a distribution of results when making repetitive measurements.
The distribution that results due to truely random events is called a "normal error" or Gaussian
curve. It is also sometimes called a "bell-shaped curve". The mathematical expression for this
random distribution is:

Where is the population standard deviation:

and with µ being the population mean.

This equation is plotted below. The dark vertical lines indicate the area under the curve from -1
to +1 , and the lighter lines indicate the area under the curve for ±2 .
Related topics:
 data handling

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Spectroscopic Lineshapes
Introduction
The width and shape of spectroscopic transitions will affect the ability to extract qualitative and
quantitative information from a spectrum. The lineshapes of spectroscopic transitions depend on
the broadening mechanisms of the initial and final states, and include natural broadening,
collisional broadening, power broadening, and Doppler broadening. Natural, collisional, and
power broadening are homogeneous mechanisms and produce Lorentzian lineshapes, and
Doppler broadening is a form of inhomogeneous broadening and has a Gaussian lineshape. The
general form of Lorentzian and Gaussian lineshapes are shown below. Combinations of
Lorentzian and Gaussian lineshapes can be approximated by a Voigt profile.

Gaussian and Lorentzian spectral lineshapes

Collisional or Pressure Broadening


Collisions broaden spectroscopic linewidths by shortening the lifetime of the excited states.

Power Broadening
Power broadening occurs by shortening the lifetime of the excited state due to stimulated
emission.
Doppler Broadening
Doppler broadening is due to the distribution of atomic velocities (speed and direction), which
each have a Doppler shift with respect to an observer.

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Reaction Thermodynamics
Introduction
This doucument introduces the thermodynamics of chemical reactions. To start, imagine the
following demonstration: Cold packs contain separate compartments of water and a salt such as
ammonium nitrate. When you mix the salt and water the cold pack gets cold. Such a reaction is
called an endothermic reaction.

NH4NO3 (s) NH4+(aq) + NO3-(aq) Ho = +28.1 kJ/mol

This reaction is spontaneous even though thermal energy is needed to break the ionic bonds of
the crystalline NH4NO3.

Why do endothermic reactions occur?

The driving force for the NH4NO3 reaction is the much greater disorder that is possible for the
NH4+ and NO3- ions in solution compared to these ions arranged in a solid.

We describe the disorder or randomness of a system with the entropy, S, which has units of
kJ/mol·K.

Qualitative examples:

Liquids are more disordered than solids and gases are more disordered than liquids.
At 0oC SH2O(l) > SH2O(s)
At 100oC SH2O(g) > SH2O(l)

As 90 people enter a 180-seat lecture hall, do they take seats beginning in the front row to
completely fill the front half of the room and leaving the back half of the room empty? No, the
probability of that arrangement is very, very small. The more likely arrangement is for the 90
people to more or less distribute themselves randomly in the room. This arrangement is more
probable and we could quantitate this more probable arrangement in terms of entropy.

Spontaneity and Gibbs Free Energy


The entropy must be included to predict if a reaction will be spontaneous. The total change in the
available energy of a system is called the change in the Gibbs free energy, G:

G= H-T S
Where
G is the change in Gibbs free energy (kJ/mol)
H is the change in enthalpy (kJ/mol)
T is absolute temperature in K
S is the change in entropy (kJ/mol K)

The change in enthalpy is the amount of heat or work that is transferred when an reaction occurs.

A reaction is spontaneous if G is negative, that is, the products have a lower Gibbs free energy
than the reactants.

Note that depending on the sign of H and S, the spontaneity of a reaction can be
temperature dependent.

For standard conditions of 1 atm for gases and 1 M for solutes in solution, these energies are
given an "o" superscript. The change in energy for any reaction (at standard conditions) can be
found using tabulated standard energies of formation and standard entropies.

The f subscript for the Hfo and Gfo indicates standard heats of formation. I've used the rexn
subscript to specify that the energy changes are of a reaction. This subscript is usually left off.

From tables of standard enthalpies and free energies we can calculate Ho and Go for this
reaction.
NH4NO3 (s) NH4+(aq) + NO3-(aq)
Hfo (kJ/mol) Gfo (kJ/mol)

NH4NO3 (s) -365.6 -184.0

NH4+(aq) -132.5 -79.3

NO3-(aq) -205.0 -108.7

Ho = -132.5 kJ/mol - 205.0 kJ/mol - (-365.6 kJ/mol)

Ho = +28.1 kJ/mol

Go = -79.3 kJ/mol - 108.7 kJ/mol - (-184 kJ/mol)

Go = -4.0 kJ/mol

Since Go is a negative number this reaction is spontaneous at standard concentrations. (We


also observed that this reaction was spontaneous for the salt concentrations in the cold pack,
which were probably higher than 1 M.)

Activation Energy Diagram


Recall the activation energy diagram that was introduced in the kinetics document. The model is
valid for both exothermic or endothermic reactions.

A diagram for an exothermic reaction:

^
| ________
Energy | / \
| reactants / Ea \
| __________/ __ \
| \
| \
| G \
| \ products
| __ \_________
|
|

A diagram for an endothermic reaction:

^
| ________
Energy | / \
| / \
| / \
| / \ products
| / Ea \____________
| /
| reactants / G
| ___________/ ___ ___
|
|

Ea is the activation energy and G is the chagne in Gibbs free energy (in kJ/mol).

Don't Forget the Really Big Concepts in Chemistry


Kinetics describes how quickly or slowly a reaction occurs.

Thermodynamics describes the changes in the form of energy when a reaction occurs, for
example, converting chemical energy to heat.

Equilibrium describes reactions in which the reactants and products coexist.

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Gibb's Phase Rule


Introduction
One area often encountered in thermodynamics is the description of the equilibrium state of a
system. We can describe a system as being in a reproducible equilibrium state when we can fix
as constant some number of intensive variables. As a simple example, if an evacuated container
is filled to half its volume with pure water, we would expect the system to reach equilibrium
when the temperature, T, becomes constant and uniform throughout the container. Our common
sense tells us that only this one intensive variable must be uniform throughout the system for the
system to be at equilibrium.

The Phase Rule


At equilibrium the number of independent variables (also called thermodynamic potentials) that
must be fixed is called the number of degrees of freedom, F. It is given by:

F=C-p+2

where C is the number of components and p is the number of phases in the system. For our
simple example above, there is one component and two phases, liquid water and water vapor, so
the number of degrees of freedom is:

F=1-2+2=1

As expected above, only one variable must be constant, T in the example, to determine that the
system is at equilibrium.

The number of components can sometimes be tricky to determine. If there is a fixed relationship
between chemical species, they are not separate components. For example, if sodium chloride is
added to water you would not count Na+ and Cl- as separate components. Since [Na+] equals [Cl-
], there is only one additional component, salt.

If we repeat the above example of partially filling the evacuated container using salt water, we
now have:

F=2-2+2=2

To describe the equilibrium of this system requires two degrees of freedom, for example
temperature and the concentration of the NaCl.

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Golay Equation
Introduction
The Golay equation provides the following expresion for the theoretical plate height (H):

H = B/u + Csu + Cmu

where u is the flow rate (cm/s), B is a longitudinal diffusion term, Cs is a mass transfer term for
the analyte in or on the stationary phase, and Cm is a mass transfer term for the analyte in the
mobile phase. The longitudinal diffusion is the usual diffusion due to a concentration gradient,
with analyte in a band moving through a column diffusing from the center of the band forward
and backward. The mass transfer terms depend on the diffusion coefficients for the analyte in the
stationary and mobile phases, and can be thought of as interactions that delay the analyte and
lead to band broadening. The stationary phase mass transfer term, Cs, also depends on the
thickness of the stationary phase, and the mobile phase mass transfer term, Cm, also depends on
the particle size of the packing material due to its effect on eddy diffusion.

Plot of H (and components) vs. flow rate

Note that there is an optimum flow rate to obtain the minimum theoretical plate height.

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Gravimetry
Introduction
Gravimetry is the quantitative measurement of an analyte by weighing a pure, solid form of the
analyte. Obtaining pure solids from solutions containing an unknown amount of a metal ion is
done by precipitation.

Since gravimetric analysis is an absolute measurement, it is a principal method for analyzing and
preparing primary standards. A typical experimental procedure to determine an unknown
concentration of an analyte in solution is as follows:

 quantitatively precipitate the analyte from solution


 collect the precipitate by filtering and wash it to remove impurities
 dry the solid in an oven to remove solvent
 weigh the solid on an analytical balance
 calculate the analyte concentration in the original solution based on the weight of the
precipitate

Examples of Gravimetric Lab Procedures


Gravimetric Determination of Iron

1. Determine constant weight of the crucibles


2. Oxidation of iron sample
3. Precipitation of iron hydroxide
4. Ignition of iron hydroxide to iron oxide
5. Determine constant weight of the crucibles plus iron oxide
6. Calculation of iron in the sample

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Ground State of a Diatomic Molecule


Introduction
Two atoms that can form a bond will do so to create a diatomic molecule when they approach
each other closely. We describe the energy minimum with a potential energy curve, called a
potential well.
Morse Potential
The potential energy, V(R), of a diatomic molecule can be described by the Morse potential:

where De is the well depth, R is internuclear distance, Re is the equlibrium internuclear distance
(bond length), and

e is the vibrational constant and µ is the reduced mass.

The following figure shows the ground state potential well of the H2 molecule. The curve is
calculated from the Morse potential and the energy levels are calculated using the harmonic
oscillator model with the first anharmonic correction.
Do is the dissociation energy, which is slightly different from the well depth, De. The vibrational
energy levels in this plot are calculated using the harmonic oscillator model:

where v is the vibrational quantum number, v = 0,1,2,..., and xe and ye are the first and second
anharmonicity constants, respectively. The v = 0 level is the vibrational ground state.

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Harmonic Oscillator
Introduction
Many physical systems, such as a weight suspended with a spring, experience a linear restoring
force when displaced from their equilibrium position. The mathematical expression for such a
restoring force, F, is:

k is a proportionality constant called the force constant and x is the displacement from the
equilibrium position. This relationship is called Hooke's law. For the spring example, k will be
large for a stiff spring and smaller for springs that are weaker. Similarly, if you stretch a spring
twice as far, it "springs back" with twice the force. Of course this law is valid for limited values
of x. Try stretching a spring too far and you'll find that the restoring force is no longer directly
proportional to displacement!

The potential energy, V, for a one-dimensional system is equal to the negative of the force
integrated over x:

The constant of integration depends on the physical system being modeled. For the ground state
of a diatomic molecule, as modeled below, we can set it to zero.
Harmonic Oscillator Model for a Diatomic Molecule
We can model the bond in a molecule as a spring connecting two atoms and use the harmonic
oscillator expression to describe the potential energy for the periodic vibration of the atoms. The
potential energy, V(x), of a particle moving in one dimension is given by:

where k is the force constant as above and the constant of integration is zero. We can make this
expression more useful by changing x to R-Re, where R is the internuclear distance (the distance
between atoms) and Re is the equilibrium internuclear distance (the bond length):

The following figure shows the ground-state potential energy curve (called a potential well) for
the H2 molecule using the harmonic oscillator model. Re for H2 is 0.7412 Å. There is one
obvious deficiency in the model, it does not show the energy at which the two atoms dissociate,
which occurs at 4.748 eV for the H2 molecule (1 eV = 8065.48 cm-1). At some internuclear
distance the atoms are far enough apart so that they do not "feel" each other. That is, they are
isolated and the bond is broken. A more realistic model of the potential well of a diatomic
molecule is the Morse potential, which does model the dissociation energy.
Vibrational Energies Derived from the Harmonic Oscillator
Model
In the next figure the solid blue horizontal lines show the energy levels that are calculated using
the harmonic oscillator model:

where v is the vibrational quantum number (v = 0,1,2,...). The v = 0 level is the vibrational
ground state and is the lowest horizontal line in the plot.

e is called the vibrational constant:


where µ is the reduced mass (m1m2/m1+m2). The simple harmonic oscillator provides a good fit
to energies for the lowest energy levels, but fails at higher energies.

Note that the x-axis of this figure is different from the one above. The dotted red lines shows the
energy levels calculated from:

where v and e are the same as above and xe and ye are the first and second anharmonicity
constants respectively. These correction terms provide much better match of the calculated
energies to the energies that are observed experimentally.

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High-Performance Liquid Chromatography
(HPLC)
Introduction
High-performance liquid chromatography (HPLC) is a form of liquid chromatography to
separate compounds that are dissolved in solution. HPLC instruments consist of a reservoir of
mobile phase, a pump, an injector, a separation column, and a detector. Compounds are
separated by injecting a plug of the sample mixture onto the column. The different components
in the mixture pass through the column at different rates due to differences in their partitioning
behavior between the mobile liquid phase and the stationary phase.

Instrumentation
Solvents must be degassed to eliminate formation of bubbles. The pumps provide a steady high
pressure with no pulsating, and can be programmed to vary the composition of the solvent during
the course of the separation. The liquid sample is introduced into a sample loop of an injector
with a syringe. When the loop is filled, the injector can be inject the sample into the stream by
placing the sample loop in line with the mobile phase tubing. The different types of HPLC
columns are described in a separate document. The presence of analytes in the column effluent is
recorded by detecting a change in refractive index, UV-VIS absorption at a set wavelength,
fluorescence after excitation with a suitable wavelength, or electrochemical response. Mass
spectrometers can also be interfaced with liquid chromatography to provide structural
information and help identify the separated analytes.
Schematic of an HPLC instrument

Picture of an HPLC instrument

Close-up photos of column and injector

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Electron Microscopy
Introduction
Electron microscopy is an imaging technique that uses an electron beam to probe a material.
Since the wavelength of an electron is much smaller than the wavelength of visible light,
diffraction effects occur at much smaller physical dimensions. The imaging resolution in electron
microscopy is on the order of 1 nm, which is much better than the µm resolution of light
microscopy. When electrons penetrate a sample, they are diffracted to form a diffraction pattern.
This diffraction pattern can be transformed with a lens to obtain the sample image. Electron
microscopy finds its widest use in materials science and microbiology.

Instrumentation
The use of electron beams requires that the sample be placed in a vacuum chamber for analysis.
An electron beam is produced by applying a high voltage to a hot tungsten filament, and
accelerating the emitted electrons through a high electric field, typically 10-100 keV. The
electron beam is then focused with magnetic field lenses to a typical spot diameter of 1-100 nm
on the sample.

Transmission electron microscopy (TEM)


Transmission electron microscopy (TEM) images the electrons that pass through a sample. Since
electrons interact strongly with matter, electrons are attenuated as they pass through a solid and
require the samples to be prepared in very thin sections, less than 100 nm. Specialized electron
microscopes can use electron energies on the order of a MeV to study samples as thick as 1 µm
or more. Materials samples are or for particles dispersed as a monolayer on a support grid.
Biological samples are embedded in a solid matrix and microtomed. In all cases, the sample is
placed on some type of support grid. Either the diffraction pattern or the image of the sample is
observed on a phosphor screen below the sample, and can be recorded with film.

High resolution electron microscopy (HREM)


High resolution electron microscopy (HREM) is a variation of TEM that uses phase-contrast
microscopy to achieve a resolution of approximately 0.2 nm, which is sufficient to provide
atomic-scale resolution. The phase-contrast method uses the phase difference of multiple
diffracted beams in addition to the intensity of the diffracted beams. The lattice image that is
reconstructed is valid only when the electron beam has a spatial resolution of approximately 0.2
nm and the sample is thin enough that electrons are not scattered multiple times (less than
approximately 10 nm). Under these conditions the reconstructed lattice image represents the true
structure.

Scanning electron microscopy (SEM)


Scanning electron microscopy (SEM) uses the secondary electrons that are ejected from a sample
to image a surface. These images are useful for studying surface morphology or measuring
particle sizes. The electron beam is rastered across the sample by ramping the voltages on x- and
y-deflection plates through which the electron beam passes (the z axis is the electron-beam
direction). A detector above the sample detects the secondary electrons to produce an intensity
map as a function of electron-beam position, which is displayed on a video or computer screen.
Nonconductive samples require an evaporated gold or graphite coating over the sample to
prevent charging effects that would distort the electric fields in the electron microscope.

A recent innovation in scanning electron microscopy is to use several stages of differential


pumping between the electron gun and the sample, which is placed in a vacuum of a few torr.
This method is called environmental scanning electron microscopy (E-SEM) and allows imaging
of samples that would quickly vaporize in a high-vacuum environment.

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High-Resolution Laser Spectroscopy


Introduction
The electronic spectra of atoms and molecules are broadened by various mechanisms. This
broadening obscures features in the spectra, and can be especially problematic in trying to make
quantitative measurements in mixtures of molecules.

Instrumentation
High-resolution spectroscopy requires the narrow-bandwidth excitation sources that are only
achievable with lasers. Studies in the visible spectral region typically use a tunable dye laser and
studies in the near-ultraviolet and near-infrared are becoming more common as frequency-
doubling and wave-mixing methods improve. Near-infrared diode lasers are also used for high-
resolution vibrational spectroscopy.

Atomic Methods
Gas-phase atoms are inhomogeneously broadened due to the random motion of the atoms.
Narrowed lines can be obtained with counterpropogating beams, as described in a separate
document on Doppler-free laser spectroscopy. Removing Doppler broadening allows
measurement of the natural linewidth, and shows any underlying fine structure such as isotope
shifts, hyperfine splitting, and Zeeman splitting.

Atoms or atomic ions in solids will also be broadened due to the random variations of the
environments they occupy. This broadening can be reduced by fluorescence-line narrowing
(FLN) or hole-burning methods.

Molecular Methods
High-resolution studies require cooling of the molecules to remove spectral congestion and to
reduce the Doppler width of the transitions. Gas-phase studies use free-jet expansions or
molecular beams to cool molecules to very low temperatures. Large molecules are commonly
dissolved in a suitable solvent and cooled to cryogenic temperatures to form a glass or crystalline
matrix.

Collimated beam

Preparing molecules in a collimated beam greatly reduces the distribution of velocities


perpendicular to the beam direction. The beam is produced by effusion through a pinhole and a
skimmer, and the laser direction must be perpendicular to the direction of the beam. Since the
velocity component parallel to the laser is greatly reduced the Doppler width is likewise reduced.

Low-temperature matrices

Samples that can be doped into high-quality crystals can be cooled to very low temperatures in
liquid nitrogen (77 K) or liquid helium (4.2 K). Samples that are frozen in some glasses
(Sphol'skii matrices) will also show very narrow spectral lines.
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Lamps
Introduction
Lamps convert electrical energy into radiation. Different designs and materials are needed to
produce light in different parts of the electromagnetic spectrum. The following sections describe
several different types of lamps that are useful in spectroscopy.

Blackbody Sources
A hot material, such as an electrically-heated filament in a light bulb, emits a continuum
spectrum of light. The spectrum is approximated by Planck's radiation law for blackbody
radiators:

B = {2h 3/c2}{1/exp(h /kT)-1}


where h is Planck's constant, is frequency, c is the speed of light, k is the Boltzmann constant,
and T is temperature in K.

The most common incandescent lamps and their wavelength ranges are:
tungsten filament lamps : 350 nm - 2.5 µm
glowbar : 1 - 40 µm
Nernst glower : 400 nm - 20 µm

Tungsten lamps are used in visible and near-infrared (NIR) absorption spectroscopy and the
glowbar and Nernst glower are used for infrared spectroscopy.

Discharge Lamps
Discharge lamps, such as neon signs, pass an electric current through a rare gas or metal vapor to
produce light. The electrons collide with gas atoms, exciting them to higher energy levels which
then decay to lower levels by emitting light. Low-pressure lamps have sharp line emission
characteristic of the atoms in the lamp, and high-pressure lamps have broadened lines
superimposed on a continuum.
Common discharge lamps and their wavelength ranges are:
hydrogen or deuterium : 160 - 360 nm
mercury : 253.7 nm, and weaker lines in the near-uv and visible
Ne, Ar, Kr, Xe discharge lamps : many sharp lines throughout the near-uv to near-IR
xenon arc : 300 - 1300 nm

Deuterium lamps are the uv source in UV-vis absorption spectrophotometers. The sharp lines of
the mercury and rare gas discharge lamps are useful for wavelength calibration of optical
instrumentation. Mercury and xenon arc lamps are used to excite fluorescence.

Hollow-cathode Lamps
Hollow-cathode lamps are a type of discharge lamp that produce narrow emission from atomic
species. They get their name from the cup-shaped cathode, which is made from the element of
interest. The electric discharge ionizes rare gas atoms, which are accelerated into the cathode and
sputter metal atoms into the gas phase. Collisions with gas atoms or electrons excite the metal
atoms to higher energy levels, which decay to lower levels by emitting light.

Schematic of a hollow-cathode lamp

Hollow-cathode lamps have become the most common light source for atomic absorption (AA)
spectroscopy. They are also sometimes used as an excitation source for atomic-fluorescence
spectroscopy (AFS).

Related Topics
 Optics
 Optical Materials

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Harmonic Oscillator
Introduction
Many physical systems, such as a weight suspended with a spring, experience a linear restoring
force when displaced from their equilibrium position. The mathematical expression for such a
restoring force, F, is:

k is a proportionality constant called the force constant and x is the displacement from the
equilibrium position. This relationship is called Hooke's law. For the spring example, k will be
large for a stiff spring and smaller for springs that are weaker. Similarly, if you stretch a spring
twice as far, it "springs back" with twice the force. Of course this law is valid for limited values
of x. Try stretching a spring too far and you'll find that the restoring force is no longer directly
proportional to displacement!

The potential energy, V, for a one-dimensional system is equal to the negative of the force
integrated over x:

The constant of integration depends on the physical system being modeled. For the ground state
of a diatomic molecule, as modeled below, we can set it to zero.

Harmonic Oscillator Model for a Diatomic Molecule


We can model the bond in a molecule as a spring connecting two atoms and use the harmonic
oscillator expression to describe the potential energy for the periodic vibration of the atoms. The
potential energy, V(x), of a particle moving in one dimension is given by:

where k is the force constant as above and the constant of integration is zero. We can make this
expression more useful by changing x to R-Re, where R is the internuclear distance (the distance
between atoms) and Re is the equilibrium internuclear distance (the bond length):
The following figure shows the ground-state potential energy curve (called a potential well) for
the H2 molecule using the harmonic oscillator model. Re for H2 is 0.7412 Å. There is one
obvious deficiency in the model, it does not show the energy at which the two atoms dissociate,
which occurs at 4.748 eV for the H2 molecule (1 eV = 8065.48 cm-1). At some internuclear
distance the atoms are far enough apart so that they do not "feel" each other. That is, they are
isolated and the bond is broken. A more realistic model of the potential well of a diatomic
molecule is the Morse potential, which does model the dissociation energy.

Vibrational Energies Derived from the Harmonic Oscillator


Model
In the next figure the solid blue horizontal lines show the energy levels that are calculated using
the harmonic oscillator model:
where v is the vibrational quantum number (v = 0,1,2,...). The v = 0 level is the vibrational
ground state and is the lowest horizontal line in the plot.

e is called the vibrational constant:

where µ is the reduced mass (m1m2/m1+m2). The simple harmonic oscillator provides a good fit
to energies for the lowest energy levels, but fails at higher energies.

Note that the x-axis of this figure is different from the one above. The dotted red lines shows the
energy levels calculated from:
where v and e are the same as above and xe and ye are the first and second anharmonicity
constants respectively. These correction terms provide much better match of the calculated
energies to the energies that are observed experimentally.

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