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NMAT 2017

By: Kathleen Mae T. Gaspalinao


Divisions of Analytical Chemistry
! Qualitative Analysis – What is in the sample?
! Quantitative Analysis – How much of the analyte is
in the sample?

! Analyte – the component of a sample that is to be


determined.
! Ex.) iron in ground water, ascorbic acid in vitamin C
tablet, protein in milk, etc.
Errors in Chemical Analyses
! Accuracy – the closeness of the measured value to
the true or accepted value. This is expressed as error
or percent error.
! Precision – describes the reproducibility of
measurements. The closeness of the results.
Standard deviation, variance and coefficient of
variation are widely used to describe the precision
of a set of replicate data.
Determination of the boiling Point of H2O

Group 1 Group 2 Group 3 Group 4


Temp., Temp., Temp., Temp.,
Trial Trial Trial Trial
°C °C °C °C

Trial 1 99.7 Trial 1 88.2 Trial 1 99.5 Trial 1 87.4

Trial 2 99.2 Trial 2 87.9 Trial 2 101.5 Trial 2 90.0

Trial 3 99.3 Trial 3 90.0 Trial 3 98 Trial 3 95.0


Types of Errors in Experimental Data
1. Random or Indeterminate Error – an error that is
inherent in every analysis or experiment. This is
due to some uncontrollable factors affecting the
results. This affects measurement precision.
2. Systematic or Determinate Error – this causes the
results to be too high or too low. Hence, affecting
the accuracy of the measurement. Types:
Instrument, Method and Personal.
3. Gross Errors – human errors, resulting to outliers.
Example: writing down 100 instead of 1.00
1-8
Parallax refers to the change in the apparent position
of an object when viewed from different points.
Replicates – are samples of about the same
size that are carried through an analysis in
exactly the same way and the same time.
Outlier – a result that differs significantly
with others in the set of data.
Outlier example
Measurements: 1.123, 1.321, 1.213, 4.234
How Do We Measure and Express Errors?
1. Absolute Error, E – the difference between the
measured value and the true or accepted value,
including the sign.
Example
Boiling point of water = 100.0 °C
Laboratory measurement = 98.6 °C
E = xi – xt = 98.6 – 100.0 = -1.4 (low measurement)
!xi is the measurement during the experiment
!xt is the true or accepted value
The Representative of the Measurements
1. Mean – average or arithmetic mean
! add all the measurements and divide
the sum by the number of measurements
there are.
2. Median – the middle value in a set of
data that has been arranged in numerical
order.
! Arrange the measurements in ascending
order. The measurement in the middle is
the median. If the number of
measurements is an even number, arrange
the measurements in ascending order, get
the average of the 2 middle values.
1. What is the mean value for the data set listed
below?
1.1668, 1.1559, 1.1833, 1.1622, 1.1713
A. 1.1668 C. 1.1679
B. 1.1671 D. 1.1713

= (1.1668) + (1.1559) + (1.1833) + (1.1622) + (1.1713)


2
= 1.1679
2. What is the median value for the
data set shown in question 1?
A. 1.1668 C. 1.1677
B. 1.1622 D. 1.1713

1.1559, 1.1622, 1.1668, 1.1713, 1.1833


3. An error in a measurement that is equal to the
numerical difference between an experimental
value and the true or accepted value.
A. Relative ErrorC. Precision
B. Absolute Error D. Average

4. A measurement of the agreement between an


analytical result and the true or accepted value.
A. Accuracy C. Precision
B. Absolute error D. Relative error
5. A number obtained by summing the values in a
set and dividing the sum by the number of data
points in the set.
A. Bias C. Standard Deviation
B. Average D. Gross Error
6. It is the central value in a set of replicate
measurements.
A. Mean C. Median
B. Range D. Standard deviation
The Mole Concept
The Mole
1 mole (n) of any substance contains 6.023 x 1023
particles
Particles = Atoms, Ions, Isotopes, Molecules,
Formula units

1 mole of Fe contains 6.023 x 1023 Fe atoms


1 mole of Na+ contains 6.023 x 1023 of Na+ ions
1 mole of C6H12O6 contains 6.023 x 1023 of
C6H12O6 molecules
1 mole of NaCl contains 6.023 x 1023 of NaCl
formula units
Gram-Mole Conversions
!mol, n ! gram, g: use molar mass (g/
mol) as the conversion factor

!g ! mol: use the inverse of the molar


mass (mol/g) as the conversion factor
Common Conversion Factors
!Molar mass
!Stoichiometric
relationships
!Molecular formula
!Molar mass of sodium is 23 grams/
mole
!As a conversion factor:
!Molecular formula as a
conversion factor:C6H8O6
!Stoichiometric relationships as
conversion factor:
3H2(g) + N2(g) ! 2NH3(g)
Try!
!In the synthesis of ammonia from
hydrogen and nitrogen gases, how
much grams of nitrogen gas is
needed to produce 5.0 grams of
ammonia?

3H2(g) + N2(g) ! 2NH3(g)


8. One mole of oxygen contains this
number of atoms.
A. 1.24 x 1024 C. 6.022 x 1012
B. 6.022 x 1023 D. 6.022 x 10-23
9. Calculate the molar mass of (NH4)3AsO4. Atomic
masses are:
N = 14 H=1
O = 16 As = 75

A. 417.80 g/mol C. 193.03 g/mol


B. 165.02 g/mol D. 156.96 g/mol
Solutions and
Concentrations of
Solutions
Aqueous Solutions
- Solutions with water as the solvent.
Components of Solutions
1.Solute – the substance present in lesser
amount. The substance being dissolved.
2.Solvent – the substance present in greater
amount. The substance that dissolves.

Solution = solute + solvent


Concentrations of Solutions
- Expresses the amount of solute contained in a
solution
1. Molarity, M – the number of moles of solute in 1
liter of solution.
M = mol solute/ L solution
0.10 M NaCl solution = 0.10 molar NaCl solution
=0.10 moles NaCl in 1 L solution
= 0.10 mol NaCl/L solution
= 0.10 mol/L
= 0.10 mmol NaCl/mL solution
! Parts per thousand, ppt = 1/1000, g/L
! Parts per million, ppm = 1/1000000, mg/L
! Parts per billion, ppb = 1/1000000000, µg/L
For acids, the eq./mol is the
number of H+ that it can furnish
when in solution.
HCl = 1 eq./mol
H2SO4 = 2 eq./mol
H3PO4 = 3 eq./mol
For bases, it is the number of OH- than it can
furnish when in solution.
NaOH = 1 eq./mol
Ca(OH)2 = 2 eq./mol

For ionic solids, it is approximated to be the charge


of the ion (drop the sign).
Na+ = 1 eq./mol
Ca2+ = 2 eq./mol
Al3+ = 3 eq./mol
! What is the normality of a solution that is made
by dissolving 2.0 g of CaCl2 in enough volume
of water such that the total volume of the
solution in 1000 mL?

! N = nM, n here is the number of equivalents,


eq.
! A solution of Ba(OH)2 has a concentration of
0.240 M. What is its normal concentration?
11. A liter of CuCl2-water solution which contains 1.0
mg of CuCl2 has a concentration of…
A. 1.0 ppb C. 1.0 ppt
B. 1.0 ppm D. none of these
12. A liter of chromium solution which contains 1.5
micrograms of chromium has a concentration of
A. 1.5 ppb C. 1.5 ppt
B. 1.5 ppm D. none of these
13. A 2.0 molal sodium chloride solution is
A. 2.0 mol NaCl in 1.0 L of solution.
B. 2.0 mol NaCl in 1.0 L water.
C. 2.0 mol NaCl in 1.0 kg solution.
D. 2.0 mol NaCl in 1.0 kg water.
16. Deedee stole from Dexter’s Laboratory a liter of 8.5%
by mass sodium hydroxide solution. What did she have?
A. 1.0 L of 8.5 g NaOH in 1.0 L solution.
B. 1.0 L of 8.5 kg NaOH in 100 kg solution.
C. 1.0 L of 8.5 g NaOH in 100 g water.
D. 1.0 L of 8.5 mg NaOH in 100 mL of water
64. The concentration of sodium chloride in blood
serum is approximately 0.14 M. What volume of
blood serum contains 2.0 g of NaCl? ( molar masses:
Na=23 g/mol, Cl=35.45 g/mol)
A. 55.8 mL C. 240 mL
B. 0.14 mL D. 20.0 mL
65. What will be the final volume of a solution
prepared by diluting 25 mL of 8.25 M sodium
hydroxide to a concentration of 2.40 M?
A. 330 mL C. 210 mL
B. 86 mL D. 60 mL
54. In a 100-mL 0.1022 M HCl solution, what is the
solvent?
A. HCl C. Ethanol
B. Organic D. Water
Equilibrium
Chemical Equilibrium
Le Chatelier’s Principle – any change in the
system at equilibrium results in the shift
of equilibrium to the direction which
minimizes the change
The change could be towards the formation
of more of the products (forward
direction) or towards the formation of
more of the reactants (reverse or backward
direction).
! At equilibrium, the rate of the forward reaction is
the same as the rate of the reverse reaction. In
other words, how fast the products form is the
same as how fast the products are converted
back to reactants. There is change but it just
seems that there is none.
! The equilibrium constant, K, is a number equal to a
particular ratio of equilibrium concentrations of
product and reactant at a specific temperature.
! The magnitude of the equilibrium constant, K, is an
indication of how far the reaction proceeds towards
forming the product.
! If K is large, lots of products are formed.
! If K is small, only few products are formed.
! The equilibrium constant is expressed in an
equation called the “equilibrium constant
expression”.
! K = the concentration of the products raised to each
of their respective coefficients all over the
concentrations of the reactants raised to their
respective coefficients.
! K values are constant at a specific temperature.
They are also dimensionless.
! In an equilibrium expression, the concentrations of
pure substances (pure solids and pure liquids) are
not included.
Write ion product constants or solubility product
constants.
Reaction Quotient, Q = the ratio of the concentrations of
the products and the reactants that may or may not be at
equilibrium.
It is used to predict which direction will the reaction
proceed, forward or backward.
It is expressed the same way as the K expression is
expressed.
16. Given the equation representing a reaction at
equilibrium:
N2(g) + 3 H2(g) → 2 NH3(g) + energy
Which changes the equilibrium to shift to the right?
A. Decreasing the concentration of H2
B. Decreasing the pressure
C. Increasing the concentration of N2
D. Increasing the temperature
40. Consider the dissolution of MnS in water.
(Ksp of MnS = 3.0 × 10-14)
MnS(s) + H2O(l) Mn2+(aq) + HS-(aq) + OH-(aq)
How is the solubility of manganese(II) sulfide
affected by the addition of aqueous potassium
hydroxide to the system?
A. The solubility will be unchanged.
B. The solubility will decrease.
C. The solubility will increase.
D. The amount of KOH added must be known before
its effect can be predicted.
! Equilibria of Sparingly
Soluble Solids
Solutions of Electrolytes
Solutions of Acids & Bases
1. Arrhenius definition
acid = substance that furnishes H+ in the solution
base = substance that furnishes OH- in the
solution
Ex.) acid = HCl, HNO3, H2SO4
base = NaOH, KOH, NH3
2. Lewis definition
acid = electron pair acceptor
base = electron pair donor

3. Bronsted-Lowry definition

acid = proton donor

base = proton acceptor

Conjugate acid-base pair
Give the conjugate base
1. HClO4 –-
2. H2S ------
3. HCO3- ---

Give the conjugate acid


1. CN- --------
2. SO4-2 ---
3. H2O ----
4. HCO3- ---
Strengths of Acids and Bases
Amphiprotic species – species that possess both
acidic and basic properties
Binary acid – an acidic substance that is composed
of 2 kinds of elements
Monoprotic acid – an acid that is composed 1
acidic hydrogen
Polyprotic acid – an acid that is composed of more
than 1 acidic hydrogen
pH – a measure of the relative acidity or
basicity of a saubstance
pH = - log [H+]
pOH = - log [OH-]
pH + pOH = 14
Auto-ionization of water
Acid-Base equilibria
Strong acids and bases – 100% ionization
Weak acids and bases – weak dissociation,
only partially dissociated
Buffer
! A solution that resists a drastic change in pH when a
small amount of strong acid or strong base is added
to it
! Components: a.) weak acid and its conjugate base
b.) weak base and its conjugate acid
TITRATIONS
Acid-Base
Titrations
! Titration – the process by which the
concentration of a known volume of analyte is
carefully measured by the addition of a known
volume of a solution of known concentration
(titrant).
! Titrant – The solution that titrates the sample.
A standard solution.
! Indicator – weak organic acid or base that
changes color at specific pH ranges .
Equivalence point – the point at which species in the
solution are stoichiometriacally equivalent.

HCl + NaOH ! NaCl + H2O

At eq. pt., 1 mol HCl = 1 mol NaOH

H2SO4 + 2NaOH ! Na2SO4 + 2H2O

At eq. pt. 1 mol H2SO4 = 2 mol NaOH


! End point – the point in the titration that may or
may not be exactly the same as the equivalence
point but nearly coincides with it. At this point, an
observable change signals the occurrence of the
equivalence point.
Strong acid – Strong base titration
Weak acid – Strong base Titration
Titration of a Polyprotic Acid
Pricipitimetry
! Precipitation titration
! Argentometry – precipitation titration that uses silver

1. Mohr Method – uses chromate as indicator


2. Volhard method – uses iron as indicator
3. Fajans method – uses dichlorofluorescein as indicator
Mohr Method
Volhard method
Fajans method
Redox Titrations
! Commonly involves potassium permanganate,
dichromate, thiosufate, and iodine solutions
! END
Thank you!

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