Chem 26 Notes

UPD
Should only be a supplement to discussions

Table of Contents*
Part 2 Introduction to Analytical
Chemistry
[A] Introduction
[1] Stoichiometry
[B] Volumetric Analysis
[1] Introduction
[2] Acid-Base Titration
[3] Precipitation Titration
[4] Complexometric Titration
[5] Redox Titration
[C] Introduction to Potentiometry
[1] General Principles
[2] Reference Electrode
[3] Indicator Electrode
[D] Introduction to Absorption
Spectroscopy
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[1] Interaction of Radiation and

Matter
[2] Radiation Absorption
[3] Instrumentation
[E] Introduction to Separation
Techniques
[1] Separation by Extraction
[2] Chromatographic Separation
[F] Equations
*(Ctrl + F the roman numeral to skip to
that part. Ex: [B.3])

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[A.1] Stoichiometry
Stoichiometry
brance regarding quantities
quantitative relationship of reactacts and products in reactions
mole/mass relationship in chemical reactions
Mole
Avogadro (6.02 x 1023)
number of atoms, molecules, ions, etc in a given gram
Gravimetric Analysis
deals with mass
compared with Volumetric
analyte
converted to insoluble ppt
isolated, and then weighed
used in ppt method
based on chemically related composition
Steps
Convert
Isolate
Weigh
% analyte

If analyte is not precipitate

but chemically related
mass and composition of related to analyte can lead to analyte
Example would be a rock sample Fe2O3(gotten) Fe (desired)

Gravimetric Factor, GF
for converting mass parameters

where
n is determined by related/same elements
Example
Sulfur in SO3-SO4

Iron in Fe3O4-Fe2O3

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Volatilization Method
quantitatively eliminate water
direct
water collected over soliddessicant
calculate mass gain
indirect
loss mass after being heated
calculate mass loss
Application
Determine moisture
Practice
correct to a dry basis
compared to sample as received
add/remove water to some reproducible level
Example: 14.57% protein, 10.4% water, etc
Equation

where
NVM is non volatile matter
Proteins is the compound desired
Note
Nonvolatile Matter = Dry
Water = Volatile

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[B.1] Introduction
Volumetric Titration
measures Volume
Titrimetry
quantitative relationship of volume reagent with known concentration consumed by analyte
Titration
slow addition of
reagent of known concentration (titrant) to
test substane (measurand)
Equivalence Point
Point in titration when amount is chemically equal to amount analyte
End Point
Point where physical change (caused by addition of indicator) associated with the condition
of chemical equivalence occurs
Techniques
Direct
analyte reacts with titrant
Cl- + Ag+ AgCl
Back
for slow reactions
use excess to speed up reaction
amount of excess used to react with analyte is determined by titration with 2nd
standardized solution

Displacement
Complexometric
EDTA

Titration Methods
Acid Base
Redox
Ppt
Complex

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[B.2] Acid-Base Titration

Acid-Base
Neutralization Reaction
H+ + OH- H2O

fast
which is ideal
Ktitrant = 1/ 1x10-14

Indicators
change in color, etc
produces observable physical change at/near eq. pt.
natural or synthetic
Weak organic acid/base that differs in color from conjugate base/acid
change color at a certain pH
determine pH it changes at

Ideally, [HIn] = [In-]

if [HIn] were yellow and [In-] were red, then solution would be orange
Determine pH of solution

at equivalence point
pH = pKa
ideally, if pH = 5, indicator pKa = 5
Color
Full acid color = pKa + 1
Full base color = pKa 1
Example
if Ka= 1x10-4
Acid color pH = 3
Base color pH = 5
Complete change in color from 3 to 5
pH range = 4 1
Reaction should occur between 3 and 5
Application
construct graph
Regions in Curve
Initial Point

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Volume = 0
Pre-equivalence Point
pH determined by x's H+/OH Volume < Eq Point
Equivalence Point
pH is dissociation of H2O

Post Equivalence
pH determined by x's titrant
Volume > Eq Point
Weak Base Strong Acid
opposite graph of Strong Base Weak Acid
use Kb
and related Henderson - Hasselbalch equation
Titration Curve
see if titration is feasible or not
most feasible is Strong Base - Strong Acid
best change in pH at equivalence point
steep curve
if Ka = 10-8
titrationg is no longer feasible
high error, curve not steep enough
10-6 is the cutoff, though delikado pa rin
Determine appropriate indicator
Easily pinpoint eq pt or pH at eq pt
Kjeldahl Method
determine organic nitrogen
protein analysis
fertilizer
Steps
Sample (Bound N)
+ Conc H2SO4,

NH4+

+ x's Strong Acid

NH3, liberated

+ Back titrated with standardized base

Soda Ash
double indicator
like in lab

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[B.3] Precipitation Titration

Precipitation Titration
form precipitate
ionic compound of limited solubility
Slow process
limited Application
AgNO3

most important precipitation reagent

precipitates halides, halide-like (SCN, CN, CNO), mercaptans( Thiols, Fatty Acids), etc
Argentometric Titration
lowest Ksp
lowest on pAg vs V
highest on pX vs V
most amount precipitated
Low Ksp, high Ktitration, Complete reaction, better pAg/V, steeper slope
Classification based on Indicator
Mohr
Titrant Ag, CrO42

Red Precipitate
Equation
mol Analyte = mol Ag
Ag + Cl AgCl(s)

Volhard
Titrant SCN-, Fe3+
Red Complex
Equation
mol Analyte = mol (x's Ag Unreacted Ag)
Ag (x's) + Cl AgCl(s)

2Ag + CrO2 Ag2CrO4(s)

SCN + Ag (unreacted) AgSCN(s)

SCN + Fe3+ Fe(SCN)2+

Fajan
Titrant Ag, DCF
DCF = Dichlorofluorescein Yellow green
Red compound adsorbed on surface
Equation
mol Analyte = mol Ag
Ag + Cl AgCl(s)
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DCF- + Cl- NVR

AgCl is a coloid, AgCl|Cl- x DCFEnd point is AgCl|Ag+ DCF-

Name

Titrant

Equation

Result

Mol Analyte

Mohr

Ag, CrO42-

Ag + Cl AgCl(s)

Red Ppt

mol Analyte = mol

Ag

Red Complex

mol Analyte = mol

Ag x's mol Ag
unreaced

Red compound
adsorbed on
Surface

mol Analyte = mol

Ag

2Ag + CrO2
Ag2CrO4(s)
Volhard

SCN-, Fe3+

Ag (x's) + Cl
AgCl(s)
SCN + Ag
(unreacted)
AgSCN(s)
SCN + Fe3+
Fe(SCN)2+

Fajan

Ag, DCF

Ag + Cl AgCl(s)
DCF- + Cl-
NVR

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[B.4] Complexometric Titration

Complex Formation Titration
EDTA
6 donor atoms
good complex
# mol Mn+ = n # mol EDTA
Mn+ + H2Y2- MY4-n + 2H+
Graphs
pM vs V EDTA
Equivalence Point
Pre Eq Pt
x's Mn+
Post Eq Pt
x's EDTA
Higher Kf, higher on graph, steeper curve
pH affects curve
there is an optimal pH
ex: pH 10 for Ca, steep enough curve
Higher pH, pH = 12, is too basic and may cause Metal oxides
Hardness of Water
like in experiment
Liebig Titration of Cyanide with AgNO3

2CN- + Ag+ Ag(CN)2-

Different from precipitation

result is a complex
different stoich
1 mol CN = 2 mol Ag
End point
turbidity
Ag+ + Ag(CN)2- 2AgCN(s)

Ag+ + Ag(CN)2- Ag[Ag(CN)2](s)

Has KI, NH3

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[B.5] Redox Titration

Redox Titration
Determination of Fe

Note
Fe3+ has to be prereduced if you want to measure ALL iron present
use SnCl, James, Walden
can be direct or indirect
uses stoich factor either
Oxidants
MnO4- Mn2+

Ce4+ Ce3+
Cr2O72- Cr3+

Iodine (Iodimetry)
less powerful than rest
limited stability
dissolves in iodide solution
Similar electro chemistry
E0 = 0.536V
I2 + 2e- 2I

I3- + 2e- 3I-

Indicator
Starch
turns solution blue
Application
ascorbic acid
sulfur compounds
Karl Fisher Method
Moisture content
evap H2O w/ heat (oven)
but if sensitive, Karl Fisher
unstable
Karl Fisher
oxidation of SO2 by I2

solids and organic liquids

Iodide (Iodometry)
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stronger the Fe
Uses
Copper

Peroxide

Ozone

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[C.1] General Principles

Potentiometry
Parts
Reference Electrode
Eref
Salt Bridge
Ej
Analyte Solution
Indicator Electrode
Eind
Equation
Ecell = Ein Eref + Ej

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[C.2] Reference Electrode

Reference Electrode
accureately known
independent of concentration
anode

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[C.3] Indicator Electrode

Indicator Electrode
Highly specific
potential depends on activity, concentration
Cathode
Calomel
SCE
Hg/Hg2, Cl2,

Silver/ Silver Chloride

responds to change of analyte

Types
Metallic
Metallic electrodes of the 1st kind
pure metal
direct equivalence with cation
single reaction
Ag/Ag+, Hg/Hg22+, etc

responds to cations
Equation

where
n is the oxidation number
Graph
Eind vs pM
looks like \
slope
m= (-)0.0592/n
y-int = E0m

2nd Kind
response to anions that are sparingly soluble
Equation

Graph
looks like /
slope
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m= 0.0592/n

Inert
carbon,etc
Membrane Indicators
Glass
for pH, sensitive

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[D.1] Interaction of Radiation and

Matter
Analytical Chem\

[D.2] Radiation Absorption

Analytical Chem\

[D.3] Instrumentation
Analytical Chem\

[E.1] Separation by Extraction

Analytical Chem\

[E.2] Chromatographic Separation

Analytical Chem\

[F] Equations
Topic

Name

Purpose

Equation

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