a.
Complete/Ultimate Analysis – amount of each
CHEM 28 – ANALYTICAL CHEMISTRY
Analytical Chemistry – involves separating, identifying, and
determining amount(s) of component(s) in a sample
Sample – material of interest to be analyzed
Analyte – substance being determined in a sample
Titrant – standard solution of known concentration
2 Areas of Analytical Chemistry:
1. Qualitative Analysis – identification of substance
2. Quantitative Analysis - measurement of amount of a
particular substance in the sample
Classification of Quantitative Analysis:
A. Based on the type of Analytical Method
a. Classical (Stoichiometric) Methods – “Wet
Analysis”
1. Gravimetric – amount of analyte determined from
amount formed
2. Volumetric (Titrimetric) – amount of analyte
determined from measured volume of titrant
4 Types of Volumetric Analysis:
1. Acid-Base Titration
2. Precipitation Titration
3. Complexometric Titration
4. Redox Titration
b. Instrumental (Non-Stoichiometric or
Physiochemical) Methods – “Modern Analysis” –
some measurable physical property is taken as a
measure of amount of analyte that requires calibration
curve/plot
1. Spectrophotometry - applies Beer’s Law
2. Electrochemical – applies Ohm’s Law and
Potenciometry
3. Chromatographic Method – Gas Chromatograph,
High Performance Liquid Chromatograph,
Chromatogram
B. According to amount of sample analyzed – based upon
size of sample taken for analysis
a. Macro Analysis – sample weighs 0.1g or more
b. Semi-Micro Analysis – sample weighs between 10 and
100mg
c. Micro Analysis – sample weighs between 1 and 10 mg
d. Ultramicro Analysis – sample weighs on the order of ìg
e. Submicro Analysis – sample weighs less than 0.1ìg or
less
C. According to relative amount of analyte – based on
amount of analyte in relation to sample
a. Major Constituent – analyte > 1% of the sample
b. Minor Constituent – analyte ammounts to 0.01% - 1%
of the sample
c. Trace Constituent – analyte < 0.01% of the sample
D. According to Extent of Desired Analysis - based on
number and type of constituents determined and reported
component determined; amounts for each constituent
present in the sample and should represent 100% of the
sample
b. Single Component/Partial Analysis – most common; not
all constituents determined
c. Proximate Analysis – amount of certain selected
constituents in a sample is determined; similar
components are determined and grouped together
d. Kjeldall Analysis – for proteins, crude fat and crude fiber
analysis using ammonia and HCl and back titration to get
the % protein
Steps in a Quantitative Analysis:
1. Selecting a method
2. Sampling
3. Sampling Processing/Preparation
4. Eliminating Interferences
a. Interferences – species other than analyte that
affects the final measurement
b. Masking – conversion of interferences into forms
not detected by the analytical method through the
addition of a reagent that reacts with the potential
interference
c. Solvent Extraction – involves an organic phase
and a liquid phase; related to liquid-liquid extraction
which involves the removal of salt and purification
d. Chemical Derivation – involves the conversion of
the analyte to desired form and its extraction
5. Measuring Property of Analyte
6. Calculation and Interpretation of Results
Factors to be considered in Defining the Analytical
Method:
1. Nature of Analysis – elemental or molecular; repetitive or
intermittent (number of samples to be analyzed);
destructive or non-destructive; sensitivity of method
2. Restrictions due to physical and chemical properties of
species of interest – e.g. radioactive, corrosive, volatile +
sample stability
3. Potential Interference – arise from similar physical or
chemical properties of other species in the sample;
a. for separation steps – choose selective method
b. LOD – minimum concentration of analyte that can
be detected by the method
c. Sensitivity of method – measures the ability of
method to discriminate between small differences
in analyte concentration
4. Concentration range of species to be studied
5. Time available for determinations – important in
manufacturing industry due to some analysis easy in
practice but some require hours of tedious attention
6. Analytical facilities available and availability of equipment
a. Accuracy desired (reliability of analysis)
b. Cost of analysis – equipment + reagents + analyst
time
Main Steps in Chemical Analysis:
1. Sampling – selecting a representative sample of
material to be analyzed; may be manual or continuous
2. Sample Preparation
 a. Preparation of lab sample for analysis, measure mass
or volume of sample and dissolve sample in
approximate solvents using highly purified chemicals
available (more expensive) – analytical reagent grade
chemicals + deionized and distilled or triple distilled or
ultrapure H2O
b. In many analysis, a small amount of impurity can
have serious effects on the experiment
c. Have to consider also stability of solutions (analytical
reagent solution and sample) may decompose
3. Isolation of Analyte
a. sample treatment (conversion of analyte to
measurable form)
b. interfering substances removed in this step or
converted to noninterfering forms or remove analyte
from rest of sample
c. do analytical separations such as precipitation,
electrolysis, solvent extraction, ion exchange and
chromatography
4. Determination Step (Measurement)
a. Utilize appropriate analytical method for routine
analysis - usually instrumental methods
b. To have confidence in analytical procedure – can
method using reference standards (samples similar in
composition to unknown sample and with precisely
known content of constituent to be determined) e.g.
highly reliable standard materials usually used for
instrumental methods
c. Standards treated in the same way as unknown –
special standard is ideally zero result
d. Blank – simulated unknown that contains none of the
analyte being determined; gives a check on reagents
used in analytical procedure
5. Calculation and Interpretation of Result
a. Make blank corrections using the blanks
Lot – total material from which samples are taken
Bulk/ Gross Sample – material taken from the lot for analysis
for archiving (study for future references)
Aliquot – small test portions of lab samples used for individual
analysis
Lot
Representative Bulk
Sample
Homogenous Laboratory
Sample
Aliquot
Random Sampling – for highly segregated materials (with
different regions for different compositions) get representative
composite sample
Sample Preparation – reduction of sample particle size by
crushing and grinding, then screening/sieving to desired
Analytical Subsample – Extract/Digestate – Analysis – Result –
Field Subsample – Field Sample – extrapolation of analytical
result back to decision unit – Decision Unit
MOISTURE IN SAMPLES
A. Forms of Water in Solids
1. Essential Water – water that is an integral part of a
solid chemical compound; exists in stoichiometric
amount
a. Water of Crystallization – in stable solid hydrate
e.g. CaC2O4⋅2H2O; BaCl2⋅H2O
b. Water of Constitution – water formed when
pure solid is decomposed by heat or other
chemical treatment e.g. Ca(OH)2(s) Ä→ CaO(s) +
H2O(g) and 2KHSO4(s) Ä→ K2S2O7(s) + H2O(g)
2. Nonessential Water – water that is physically
retained as a solid; does not occur in
stoichiometric amount
a. Adsorbed Water – water retained on the surface
of solids
b. Sorbed Water – held as condensed phase in
interstices or capillaries of colloidal solid like
starch, protein, charcoal and silica gel; often in
large amount
c. Occluded Water – entrapped in microscopic
pockets spaced irregular throughout solid
crystals; in rocks and minerals
Moisture Determination:
1. Oven Drying
a. Simplest procedure
b. Drying at 105°C – remove bulk H2O
c. Drying at 180°C – remove almost all occluded H2O
and water of crystallization
d. Sample heated at 100°C – determines weight loss in
solid sample
2. Use of Moisture Balance – analytical balance with heart
source
3. Chemical Methods – like Karl Fisher Method (non-
gaseous Titration), make use of chemical reactivity of H2Ol
used in pharmaceuticals, food and hard candy
a. Analysis made on sample as received – H2O as part
of the sample’s composition
b. Analysis on a dried basis – H2O removed usually by
drying
%𝑋 %𝑋
=
%𝑁𝑉𝑀'( *+,+-.+/ %𝑁𝑉𝑀1.+2 /*-+/
Where x is the nonvolatile analyte and NVM is nonvolatile
matter
Dissolving and Decomposing the Sample: 𝐹𝑊
𝐸𝑊 =
𝑛+9+,;*12(
Use solvent of progressively increasing selectivity solvents for
dissolving sample: 𝐺=K = 𝑀 × 𝑉=< × 𝑀𝑊 = 𝑁 × 𝑉=< × 𝐸𝑊
1. H2O Determination of Equivalent Weights:
2. Aqueous Solutions of Common Acids and Bases 1. In Neutralization Reactions – EW of substance
3. Aqua Regia: 3V HCl = 1V HNO3 participating in the neutralization reaction is the amount of
substance that either reacts with or supplies 1 mol of H+
Decomposing Samples: ions in that reaction
1. With inorganic acids in open vessels like OHs, HCl, 𝐹𝑊L
𝐸𝑊L =
HNO3, H2SO4 or HClO4 (potential explosive nature) # 𝑜𝑓 𝐻 𝑎𝑡𝑜𝑚𝑠 𝑡𝑜 𝑏𝑒 𝑓𝑟𝑒𝑒𝑑 𝑢𝑝
a. Wet Ashing – process of oxidation decomposition of 2. In Redox Reaction – Ew of a participant is that amount
organic samples by liquid OHs or mixture (hot plate, that reacts with or provides one mole of the reacting cation
beaker, watch glass in hood) at least 3 days if it is univalent, ½ mole if it is divalent and 1/3 mole if it is
trivalent. The cation referred to is the cation directly
2. Microwave Decomposing/ Digestion – either closed or
involved in the analytical reaction
open vessels – higher pressure and temperature
achieved; easy to autonate (a few minutes process but Percent Composition:
expensive equipment) 𝑔(19:;+
%𝑤 = × 100
3. High-Temperature Ignition in air or oxygen – crucibles 𝑔(19:;-12
in a furnace; dry ashing, combustion tube methods or
𝑉(19:;+
combustion with oxygen in sealed container %𝑣 = × 100
𝑉(19:;-12
4. Fusion in molten salt media sample mixed with the 𝑤 𝑔(19:;+
flux. An alkali metal salt ion heated at high temperature % = × 100
𝑣 𝑉=<(19:;-12
(300-1000°C) in Platinum crucibles where the amount of
flux >10x sample mass Parts per Million and Parts per Billion for Solids:
Common Fluxes: 𝑔(:W(;'2,+
𝑝𝑝𝑚 = × 10Y
𝑔('=X9+
1. Alkali Metal carbonates, hydroxides, peroxides and
borates – basic fluxes for acidic materials 𝑔(:W(;'2,+
𝑝𝑝𝑏 = × 10Z
𝑔('=X9+
2. Acidic Fluxes – pyrosulfates, acrid fluorides and boric
oxide For Dilute Aqueous Solutions:
3. Oxidizing Fluxes – Sodium Peroxide 𝑚𝑔(19:;+
𝑝𝑝𝑚 =
𝑉<(19:;-12
4. Na2CO3 – used for silicates and other refracting oxides
𝑔(19:;+
𝑝𝑝𝑏 =
𝑉<(19:;-12
Concentration of Solutions: 𝑝𝑋 = − 𝑙𝑜𝑔 𝑙𝑜𝑔 𝑋
Molarity – number of moles of solute over liters of solution Titer – mass of a pure substance which is chemically
#𝑚𝑜𝑙𝑠(19:;+ #𝑚𝑚𝑜𝑙𝑠(19:;+ equivalent to or reacts with a fixed volume of solution (usually
𝑀3 = = 1 mL)
𝑉<(19:;-12 𝑉=<(19:;-12
Analytical Molarity/Formality – total number of moles solute, Dilution Formula:
regardless of its chemical state in 1L solution 𝑀,12,+2;*';+/ × 𝑉,12,+2;*';+/ = 𝑀/-9:;+/ × 𝑉/-9:;+/
Equilibrium Molarity – molar concentration of a particular
species in solution at equilibrium
Normality – number if equivalents of solute/liters of solution
#𝑚𝑜𝑙𝑒𝑠 𝐺(19:;+
𝑀 = =
𝑉< 𝑉< × 𝑀𝑊(19:;+
#𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝐺(19:;+
𝑁 = =
𝑉< 𝑉< × 𝐸𝑊(19:;+
𝐺
#𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 = 𝑁 × 𝑉< =
𝐸𝑊
𝑁 = 𝑛+9+,;*12( 𝑀
 STOICHIOMETRY: Volatilization Gravimetry – analyte converted to a gas of
known chemical composition
Consider the stoichiometric reaction:
Electrogravimetry – analyte separated by deposition on an
𝑎𝐴 + 𝑏𝐵 ↔ 𝑐𝐶 + 𝑑𝐷
electrode and mass of the deposited product used to measure
In Volumetric Analysis, consider only the analyte and the titrant analyte concentration
(A and B in the stoichiometric reaction) Requirement of Gravimetry:
Mole Approach: 1. Reaction should be complete and quantitative
𝑎 2. Substance weighed should be pure and of definite
#𝑚𝑜𝑙𝑒𝑠 𝐴 = # 𝑚𝑜𝑙𝑒𝑠 𝐵
𝑏 chemical composition
3. Precipitating solution should have sufficiently low
Mmol Approach:
solubility
𝑎 4. Precipitate is easily filterable and washable
#𝑚𝑚𝑜𝑙𝑒𝑠 𝐴 = # 𝑚𝑚𝑜𝑙𝑒𝑠 𝐵
𝑏
Outline of Gravimetric Procedure:
Equivalent Approach:
1. Accurate Weighing of Sample
#𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝐴 = #𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝐵 2. Dissolution of Weighed Sample
3. Removal of Interfering Species
meq Approach:
4. Adjustment of experimental environment
#𝑚𝑒𝑞 𝐴 = #𝑚𝑒𝑞 𝐵 5. Addition of experimental environment
6. Separation of precipitate from solution
A is either solid or liquid: 7. Washing of precipitate
If A is liquid: 8. Drying of precipitate to constant weight
9. Determination of amount of analyte in sample using
#𝑚𝑜𝑙𝑒𝑠 𝐴 = (𝑀 × 𝑉< )e stoichiometry
#𝑚𝑚𝑜𝑙 𝐴 = (𝑀 × 𝑉=< )e Formation of Precipitate:
#𝑚𝑒𝑞 𝐴 = (𝑁 × 𝑉=< )e Ions in solution (10-8 cm) → Colloidal Particles (10-7 to 10-4 cm
– electrically charged) → precipitate (>10-4 cm)
If A is solid:
𝐺e (K) Stages of Formation of Precipitate:
#𝑚𝑜𝑙𝑒𝑠 𝐴 =
𝑀𝑊e ( K )
𝑀m + 𝑋 n ↔ 𝑀𝑋(()
=19+

𝐺e (=K) 1. Supersaturation
#𝑚𝑚𝑜𝑙 𝐴 = 2. Nucleation – clustering of M+ and X- ions ton form nuclei
𝑀𝑊e ( =K
)
==19 3. Particle growth or x-tal growth – further growth of nuclei
𝐺e (K) Mechanism of precipitation process is still not fully understood
#𝑚𝑒𝑞 𝐴 =
𝐸𝑊e ( =K ) but quantitatively the effect of variables can be accounted for
=+f
Assumption: particle size is related to relative supersaturation
Gravimetric Analysis – based upon the measurement of the
mass of substance that has known composition and is Van Qeimarn Ratio:
chemically related to the analyte
𝑄−𝑆
𝑅𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑆𝑢𝑝𝑒𝑟𝑠𝑎𝑡𝑢𝑟𝑎𝑡𝑖𝑜𝑛 =
Precipitation Gravimetry – analyte converted to a sparingly 𝑆
soluble precipitate
Q = concentration of solute at any instant
𝑎𝐴 + 𝑟𝑅 → 𝐴𝑎𝑅𝑟(i)
S = its equilibrium solubility
𝐺e = 𝐺X × 𝐺j Particle Size of precipitate varies inversely with average
𝐺e relative supersaturation
%𝐴 = × 100%
𝐺('=X9+ Large (Q-S)/S – greater number of nuclei and smaller
precipitate particles
Gravimetric Factor – ratio of Formula Weights (FWs) used to
convert mass of one chemical formula to another based on the Smaller (Q-S)/S – smaller number of nuclei and larger particles
stoichiometric relation between the two (crystalline precipitate)
𝐺(1:Kk; l1* (:W(; Nucleation vs. Cell Growth:
= 𝐺K-.+2 (:W(;
If nucleation predominates, get larger number of smaller
𝑎 × 𝐹𝑊(1:Kk; l1* (:W(;
× particles
𝑏 × 𝐹𝑊K-.+2 (:W(;
In crystal growth predominates, fewer particles of relatively
large particles are obtained (desired outcome)
Experimental Control of Particle Size (variables that Post Precipitation – phenomenon where the precipitate of an
minimize relative supersaturation): insoluble substance is followed by the gradual precipitation of
a chemically related substance which is normally soluble
1. Elevate Temperature (to increase S) - precipitate from hot
solution
2. Dilute Solution (to minimize Q)
3. Slow addition of precipitating agent with good stirring (to
lower average value of Q)
4. Adjust factors that increase solubility e.g precipitate or use
of complexing agents (more acidic, comx is much more
soluble)
5. Digestion or ageing precipitate (precipitate in contact with
mother liquor at increased temperature)
Ostwald Ripening – for crystalline precipitates
Coagulation – process of converting a colloidal suspension
into a filterable solid
Peptization – reverse process of coagulation
Ways to coagulate a colloidal suspension:
▪ Heating with stirring to decrease number of adsorbed ions
▪ Adding an electrolyte to shrink counter-ions layer so
particles are closer and agglomerate
Counter-Ion
Layer: change a
precipitate to the
Primary Adsorbed primary layer
Layer: Common Ion

Electrical Double Layer of a Colloid

Coprecipitation – the process in which a normally soluble

compound is carried out of a solution during precipitation of a
desired precipitate
4 types of Coprecipitation:
1. Surface Adsorption – common in coagulated colloids
due to large surface area; normally soluble compound
carried out of solution on the surface of a coagulated
colloid; minimized by washing with volatile electrolyte or
by reprecipitation
2. Mixed-Crystal Formation – a contaminant ion (with some
charge and almost the same size) replaces an ion in the
lattice of a crystal )e.g. PbSO4 in BaSO4 or MnS in CdS);
minimized by separating interfering ion or using a different
precipitating agent that does not give mixed-crystals with
ions in question.
3. Mechanical Entrapment – a portion of the solution is
trapped in a tiny pocket; may be minimized by employing
conditions of low supersaturation and by digestion
4. Occlusion – foreign ions in the counter-ion layer may
become trapped or occluded within the rapidly growing
crystals may be minimized by employing conditions of low
supersaturation and by digestion
Homogenous Precipitation – technique in which the
precipitating agent is chemically generated in the solution via a
slow chemical reaction; slow appearance of precipitating agent
and relative supersaturation is kept low
 EQUILIBRIA AND EQUILIBRIUM CONSTANTS OF ▪ Reaction should be quantitative (reaction should be at
IMPORTANTCE TO ANALYTICAL CHEMISTRY: least 99% complete); quantitative reaction with Keq ≥ 107
▪ Convenient method to follow progress of reaction to
For the general reaction:
determine when it is complete ( for titration: with suitable
𝑤𝑊 + 𝑥𝑋 ↔ 𝑦𝑌 + 𝑧𝑍 indicator)

[𝑌]y [𝑍]z Reaction that go to completion and suitable for chemical

𝐾 = analysis:
[𝑊]{ [𝑋]3
Dissociation of H2O: ▪ Formation of precipitate
▪ Formation of un-ionized molecules
2𝐻} 𝑂 ↔ 𝐻• 𝑂m + 𝑂𝐻 n ▪ Formation of chelates or gases e.g. strong acid + strong
base reaction
𝐾{ = [𝐻• 𝑂m ][𝑂𝐻 n ]
Effect of Electrolytes on Ionic Equilibria:
Solubility Equilibrium:
▪ For ionic participants in equilibrium reactions
𝐴3 𝐵y = 𝑥𝐴ym + 𝑦𝐵 3n
▪ Effect depends on ionic strength (ì)
𝐾(X = [𝐴ym ]3 [𝐵 3n ]y
1
Acid-Base Equilibrium: 𝜇 = ‡ 𝐶- 𝑍-}
2
Weak Acids:
Where C is the molar concentration and z is the charge
𝐻𝐴 + 𝐻} 𝑂 ↔ 𝐻• 𝑂m + 𝐴n
Electrolyte Type ì/c Examples
[𝐻• 𝑂 m ][𝐴n ] 1:1 1 KI, NaClO4
𝐾e =
[𝐻𝐴] 2:1 or 1:2 3 MgCl2, Na2SO4
2:2 4 CaSO4
Weak Base: 3:2 or 2:3 15 Fe2(SO4)3
𝐵 + 𝐻} 𝑂 ↔ 𝐵𝐻 m + 𝑂𝐻n 1:3 or 3:3 6 Na3PO4; Al(NO3)3
Effect of Electrolytes on Ionic Equilibria:
[𝐵𝐻 m ][𝑂𝐻 n ]
𝐾€ = For solutions with ì of 0.1 or less, the electrolyte is
[𝐵]
independent of the kinds of ions and dependent upon the ionic
Complex Formation Equilibrium: strength e.g. soluble BaSO4 is the same in solutions NaI,
KNO3, or AlCl3 provided the ì is the same.
e.g.𝐴𝑔m + 2𝑁𝐻• ↔ [𝐴𝑔(𝑁𝐻• )} ]m
Source of salt effect/ electrolye effect is the electrostatic
[𝐴𝑔(𝑁𝐻• )} ]m interaction and repulsive forces between electrolyte ions and
𝛽 = 𝐾‚ 𝐾} =
[𝐴𝑔m ][𝑁𝐻• ]} ions involved in an equilibrium effective concentration of ions
Oxidation Reduction Equilibrium: like Ba2+ & SO4- lesser as ì of the reactions becomes greater.

e.g.𝐹𝑒 }m + 𝐶𝑒 ƒm ↔ 𝐹𝑒 •m + 𝐶𝑒 •m Activity and Activity Coefficient:

[𝐹𝑒 •m ][𝐶𝑒 •m ] 𝑎3 = 𝛾3 [𝑋]

𝐾*+/13 =
[𝐹𝑒 }m ][𝐶𝑒 ƒm ] Where ã is the activity coefficient (which is a function of ionic
strength), [X] is the molar concentration
Distribution Equilibrium for a solute between immiscible
solvents Equilibrium Calculations yield values in better agreement with
experimental results than those using molar concentration
e.g.: 𝐼}('f) ↔ 𝐼}(1*K)
Thermodynamic Equilibrium Constant:
[𝐼} ]1*K
𝐾/ =
[𝐼} ]'f Consider the general reaction:

Chemical Reactions used in Analytical Chemistry: 𝑎𝐴 + 𝑏𝐵 ↔ 𝑐𝐶 + 𝑑𝐷

▪ Acid Base Reaction 𝑎‰, 𝑎Š/

𝐾+f =
▪ Precipitation, Gravimetric and Titration 𝑎e' 𝑎€W
▪ Redox Reactions
▪ Complex Formation [𝐶 , ]𝛾‰ , [𝐷/ ]𝛾Š / [𝐶 , ][𝐷/ ] 𝛾‰ , 𝛾Š /
𝐾+f = ' ' ∙ W W = ' W ∙ W '
[𝐴 ]𝛾e [𝐵 ]𝛾€ [𝐴 ][𝐵 ] 𝛾€ 𝛾e
Requirements for suitability of a reaction for use in
Chemical Analysis: As ci → 0, ì→0, ãi→1, and ai→[i] , Therefore Keq is in terms
of concentration only in very dilute solutions
▪ Reaction should be stoichiometric
▪ Reaction should take place rapidly e.g. 𝑋= 𝑌2 = 𝑚𝑋 2m + 𝑛𝑌 =m
 𝐾+f = 𝑎L=Œ• 𝑎Ž2•• 𝐻𝑁𝑂} + 𝐻} 𝑂 ↔ 𝐻• 𝑂m + 𝑁𝑂}n
𝐾+f = [𝑋 2m ]= [𝑌 =m ]2 𝛾L=Œ• 𝛾Ž2•• = 𝛾L=Œ• 𝛾Ž2•• ∙ 𝐾′(X 𝐶•–—˜ = [𝐻𝑁𝑂} ] + 𝑁𝑂}n ⋮ [𝐻• 𝑂m ]
Where K’sp is the concentration soluble product and Ksp is the
thermodynamic equilibrium constant
Debye-Huckel Equation – can calculate the ã theoretically
0.51𝑍3} √𝜇
− 𝑙𝑜𝑔 𝑙𝑜𝑔 (𝛾3 ) =
1 + 3.3𝑎3 √𝜇
Where ãx is the activity coefficient of X, Zx the charge of x, ì
the ionic strength of the solution and ax the effective diameter
of hydrated ion X in nanometers (10-9M)
Equilibrium Calculations to Complex Systems:
▪ Systematic approach for solving multiple-equilibrium
problems
▪ Used to illustrate effect of pH ad complex formation on
solubility where equilibria are involved
3 Types of Algebraic Equations used in solving multiple-
equilibrium problems:
1. Keq expressions – develop n independent algebraic
equations
2. Mass Balance Equations – containing n unknowns
3. A single charge-balance equation - & solve
simultaneously
A Systematic Method for solving Multiple-Equilibrium
Problems:
1. Write the balance chemical equation (for all pertinent
equilibria)
2. Set-up equation for unknown quantity ( in terms of
equilibrium concentrations)
3. Write Keq expressions for all equilibria in step 1
4. Write mass-balance expressions for the system
5. Write charge-balance expressions for the system if
possible
6. Count the number of equations and the number of
unknowns; if the number of equations ≥unknowns, then
go to step 7; if not STOP, problem unsolvable
a. Make suitable approximations (to simplify
algebra) and decide the number of unknowns
7. Solve equations for the unknown values
8. Check the validity using provisional answers→if valid,
problem solved, if not try again and approximately
recalculate
*approx. can only be made in charge-balance and mass-
balance equations can assume some terms negligible or use
computer – several software packages available for solving
multiple, nonlinear, simultaneous equations
Mass balance Equation
Mass Balance Equation: relate equilibrium concentration of
various species in a solution to 1 another and analytical
concentrations of various solutes
Total or analytical concentration of a substance is equal to the
equilibrium concentrations of its various species in a solution
e.g. HNO2 Solution
Charge-Balance Equation – apply Electroneutrality Principle
(electrolyte solutions are electrically neutral)
Total Concentration of (+) ions = total concentration of (-) ions
Molar concentrations →molar charge concentration →
multiply molar charge concentration of ion by it charge = molar
charge concentration
VOLUMETRIC ANALYSIS:
Standard Solution (Titrant) – reagent of known concentration
used in the titration
Equivalence Point – point in titration when amount of the
titrant is chemically equivalent to amount of analyte in sample:
For any titration at equivalence point:
#𝑒𝑞𝑢𝑖𝑣 𝑎𝑛𝑎𝑙𝑦𝑡𝑒 = #𝑒𝑞𝑢𝑖𝑣 𝑡𝑖𝑡𝑟𝑎𝑛𝑡
End Point – point in titration which estimates the equivalence
point by observing some physical changes associated with the
equivalence point
▪ Most common endpoint – color change due to titrant,
analyte or indicator
▪ Can use instruments to detect endpoints, e.g. if physical
property is potential or conductivity
Back Titration – process in which an excess of standard
solution is added to the analyte and excess amount of
standard determined by titration with a 2nd standard solution;
required when rate of reaction between analyte and standard
reagent is slow or when standard reagent lacks stability
Requirements for Volumetric Chemical Reaction:
▪ Reaction must proceed according to a definite chemical
reaction
▪ Reaction must be complete (Keq ≥ 107)
▪ Availability of a method to detect endpoint
▪ The reaction must be rapid
Primary Standard – an ultrapure scompound that serves as the
reference material for a titrimetric method of analysis
Requirements for a Primary Standard:
▪ High purity (~99.5% pure)
▪ Stability toward air
▪ Absence of hydrated H2O
▪ Readily available at a reasonable cost
▪ Reasonable solubility in titration medium
▪ Reasonably large molar mass or FW (minimize relative
error in weighing) with required inc’s directly with FW
Desired Properties of Standard Solutions:
▪ Sufficiently stable
▪ Reacts rapidly with analyte
▪ Reacts completely with analyte
▪ Undergo selective reaction with analyte that can be
described by a simple balanced equation
Methods to establish concentration of standard solutions:
1. Direct Method – weighed quantity of a primary standard
dissolved in suitable solvent and diluted to an exactly
known volume
2. Standardization – titrant to be standardized is used to
titrate:
a. A weighed quantity of a primary standard
b. Weighed quantity of a secondary standard
(compound whose purity was determined by chemical
analysis and serves as reference material for titration)
c. Measured volume of another standard solution
Secondary Standard Solution – titrant standardized against
a 2” standard or against another standard solution
Neutralization Titrations:
Analytes – acids or bases that can be converted to such
species by chemical treatment
Standard Solutions – strong acids or strong bases (react
more completely than their weaker counterparts
Titration Curve:
Plot some function of analyte or titrant concentration vs. Vtitrant
or instrument reading
[H3O+] ≤ 0.1 Ka for full base color
Indicator pH Range:
𝑝𝐻 (𝑎𝑐𝑖𝑑 𝑐𝑜𝑙𝑜𝑟) = − 𝑙𝑜𝑔 𝑙𝑜𝑔 (10 𝐾' ) = 𝑝𝐾' − 1
𝑝𝐻 (𝑏𝑎𝑠𝑖𝑐 𝑐𝑜𝑙𝑜𝑟) = − 𝑙𝑜𝑔 𝑙𝑜𝑔 (0.1 𝐾' ) = 𝑝𝐾' + 1
𝐼𝑛𝑑𝑖𝑐𝑎𝑡𝑜𝑟 𝑝𝐻 𝑅𝑎𝑛𝑔𝑒 = 𝑝𝐾' ± 1
(approximate pH transition range of most acid-base indicators)
Indicator Choice:
▪ Can use any indicator which could change color at the
equivalence point of the titration
▪ Equivalence point region: pH 4-10; can use any indicator
changing color in this region
▪ Smaller equivalence point region with dilution lessens
choice of indicator
BUFFER SOLUTIONS:
Buffer Solutions – a solution of a weak acid and its conjugate
base or a weak base and its conjugate acid that resists
changes in pH of a solution as a result of either dilution or
small addition of acids or bases

Stages of Titration: HA + A-:

▪ Initial point 𝐻𝐴 + 𝐻} 𝑂 ↔ 𝐻• 𝑂m + 𝐴n
▪ Pre-equivalence region [𝐻𝐴]
▪ Equivalence point 𝐻• 𝑂m = 𝐾'
[𝐴n ]
● Equivalence Point Region – large ÄpH for small
ÄV [𝐻• 𝑂m ][𝐴n ]
▪ Post equivalence region 𝐾' =
[𝐻𝐴]
Effect of Concentration on Titration Curve: Henderson – Hasselbalch Equation:
ÄpH at equivalence point region decreases as concentration [𝐴n ]
of analyte or titrant decreases 𝑝𝐻 = 𝑝𝐾' + 𝑙𝑜𝑔 𝑙𝑜𝑔
[𝐻𝐴]
Acid-Base Indicators – week, organic acid/base whose Properties of Buffer Solutions:
undissociated form differs in color from its conjugate base/acid
form. ▪ Essentially independent of dilution
▪ Resist pH change after addition of small amounts of
Typical Equilibrium Reaction: strong acids or bases
Acidic Indicator: Addition of Strong Acid or Base to Buffer solutions:
𝐻𝐼𝑛 + 𝐻} 𝑂 ↔ 𝐼𝑛 n + 𝐻• 𝑂m ▪ Addition of a strong base converts the acid into its
(acid color) (base color) conjugate base thus increasing the base and decreasing
the acid leading to a small change in the ratio and a small
Basic Indicator: ÄpH
▪ Addition of a strong acid converts the base into its
𝐼𝑛 + 𝐻} 𝑂 ↔ 𝐼𝑛𝐻 m + 𝑂𝐻 n
conjugate acid thus increasing the acid and decreasing
(base color) (acid color) the base leading to a small change in the ratio and a small
ÄpH
For HIn:
Buffer Capacity:
[𝐻• 𝑂m ][𝐼𝑛n ]
𝐾' = ▪ number of moles of a strong acid or strong base that
[𝐻𝐼𝑛]
causes 1.00L of the buffer to undergo a 1.00 unit change
[•š2]
[𝐻• 𝑂m ] = 𝐾' in pH
[š2›]
▪ depends on the total concentration of its components and
When [HIn]/[In-] ≥ 10: HIn exhibits its pure acid color also on their concentration ratio
▪ at max when ratio = 1
When [HIn]/[In-] ≤ 0.1: HIn exhibits its true base color

[H3O+] ≥ 10 Ka for full acid color

 Preparation of Buffers – a buffer solution of any derived pH Effect of Reaction Completeness:
can be prepared by combining calculated quantities of a
▪ The more complete a reaction between acid and base, the
suitable conjugate acid/base pair
larger the ÄpH at equivalence point region
Composition of Buffer Solutions as a Function of pH ( use ▪ The smaller Ka is, the higher the pH at equivalence point
of á-values): and the smaller the ÄpH
Consider acidic buffer with HA + A-: Titration Curve for Weak Base:
𝐶ž = [𝐻𝐴] + [𝐴n ] Derivation is analogous to that of a weak acid
[𝐻𝐴] [𝐻• 𝑂 m ]
𝛼 = =
𝐶ž [𝐻• 𝑂m ] + 𝐾'
[𝐴n ] 𝐾'
𝛼‚ = = m

𝐶ž [𝐻• 𝑂 ] + 𝐾'
𝛼 + 𝛼‚ = 1
Titration Curve for Weak Acids:
Consider the reaction of 50.00 mL 0.1000M HOAc (Ka = 1.75 x
105) with 0.1000m NaOH
𝐻𝑂𝐴𝑐 + 𝑁𝑎𝑂𝐻 → 𝐻} 𝑂 + 𝑁𝑎𝑂𝐴𝑐
1. Initial pH (VNaOH = 0.00 mL)
𝐻𝑂𝐴𝑐 + 𝐻} 𝑂 ↔ 𝐻• 𝑂m + 𝑂𝐴𝑐 n
[𝐻• 𝑂m ][𝑂𝐴𝑐 n ]
𝐾' = = ¡𝐾' [𝐻𝑂𝐴𝑐]
[𝐻𝑂𝐴𝑐]
pH = 2.88
2. Pre-equivalence Point
#𝑚𝑜𝑙𝑒𝑠'; +f:-.. X; − # 𝑚𝑜𝑙𝑒𝑠;-;*'2;
[𝐻𝑂𝐴𝑐] =
𝑉ž1;'9
Use either Ka expression or Henderson-Hasselbalch Equation to
find pH
pH = 4.16
3. Equivalence Point (all HOAc converted to OAc-
𝑂𝐴𝑐 n + 𝐻} 𝑂 ↔ 𝐻𝑂𝐴𝑐 + 𝑂𝐻 n
[𝐻𝑂𝐴𝑐][𝑂𝐻 n ]
𝐾' = = ¡𝐾W [𝑂𝐴𝑐 n ]
[𝑂𝐴𝑐 n ]
pOH = 5.27 pH = 8.73
4. Post Equivalence Point (excess NaOH)
# 𝑚𝑜𝑙𝑒𝑠;-;*'2; −#𝑚𝑜𝑙𝑒𝑠'; +f:-.. X;
[𝑂𝐻n ] =
𝑉ž1;'9
pOH = 4.00 pH = 10.00
Determination of Ka or Kb for weak acids or bases using
potentiometric titration (pH meter + glass pH electrode)
▪ For weak acid, at half-neutralization: pH = pKa
▪ For weak base, at half-neutralization: pOH = pKb
Effect of Concentration on Titration Curves for Weak
Acids:
▪ Initial pH values are higher and equivalence point. pH is
lower for more dilute concentrations of acid or titrant
▪ At intermediate titrant volumes, pH values differ only
slightly due to buffering action
COMPLEX ACID-BASE SYSTEMS NaHCO3 + Na2CO3:
Na2CO3
Complex Acid-Base Systems – mixture of a strong acid and
weak acid (Ka ≤ 10-4)
Concentration of approximately same order of magnitude
In early stages of titration (before 1st equivalence point);
titration curve identical to strong acid
After 1st equivalence point, remainder of titration curve identical
to that of dilute solution of weak acid
Polyfunctional Acids and Bases:
pH of Polyfunctional Systems – determined using systematic
approach to multiple equilibrium problem (solve simultaneous
equations)
Buffer Solutions involving Polyprotic Acids:
2 buffers can be prepared from weak acid H2A and its salts:
1. H2A + NaHA
2. NaHA + Na2A
pH of (2) > pH of (1)
estimate pH by assuming a single principal equilibrium and
using the Henderson-Hasselbalch Equation
Salts with both acidic and basic properties – formed during
neutralization titration of polyfunctional acids and bases
If Ka1>Kb2, solution is acidic, otherwise basic
Titration curves for Polyfunctional Acids:
Multiple endpoints observed
For titration step to be distinct Ka1/Ka2 > 103
Titration Curve for a Diprotic Acid:
Initial pH – consider only 1st dissociation step
Before 1st equivalence point – 1st Buffer region
1st Equivalence Point (with solution of salt of HM-)
After 1st equivalence point but before 2nd equivalence point
(second buffer region)
2nd equivalence point (with solution of Na2M)
pH beyond equivalence point (with excess base/ NaOH)
Titration Curves for Polyfunctional Acids and Bases:
Titration of H3PO4 – with 2 well-defined endpoints like
H2PO42-: Kb2>Kb1; can be titrated with standard acid but not
with standard base
Ttration of Carbonates and Alkali mixtures:

Substance Relation between Mmoles

volumes substance
present
NaOH V2 = 0 M x V1
Na2CO3 V1 = V2 M x V1
NaHCO3 V1 = 0 M x V2
NaOH + Na2CO3 V1>V2 NaOH:
Na2CO3:
V1<V2 NaHCO3:
 PRECIPITATION TITRATION
Effect of Concentration on Titration Curves – increase in
concentration enhances ÄpX at equivalence point region
(same trend as in acid-base titration)
Effect of Reaction Completion on Titration Curves – greatest
ÄpX I titration of ion which forms the least soluble Ag+ salt
(represents most nearly complete reaction)
Kf = 1.05 x 105
3. Fajan’s Method – make use of adsorption indicators
Adsorption Indicators – an organic compound that tends to be
absorbed unto the surface of the solid in precipitation
titration e.g fluorescein
e.g Titration of Cl- with AgNO3 which will form a colloidal
precipitate
𝐴𝑔m + 𝐶𝑙 n ↔ 𝐴𝑔𝐶𝑙(()

𝐴𝑔m + 𝑋 n ↔ 𝐴𝑔𝑋 Before Equivalence Point (with excess Cl-):

(AgCl) | Cl- | M+
1 1 After Equivalence Point (with excess Ag+):
𝐾 = =
[𝐴𝑔m ][𝑋 n ] 𝐾(X (AgCl) | Ag+ | x- / FI- (pinkish red) (can be NO3-, the indicator or
any anion)
The smaller the Ksp, the larger the K for titration
Fluorescein - adsorption indicator (HFI)
Endpoints of Argentometric Titrations: Color Change – yellow green to pinkish red; due to adsorption
process and not precipitation
Chemical - indicators Ion Product Q > Keq, precipitation
Potentiometric – pH meter; voltage converted to pH (Potential)
Amperometric – current measured by ammeter
Chemical Indicators for Precipitation Titrations:
Analyte A, Titrant B and Indicator In
Titration Reaction:
𝐴 + 𝐵 → 𝐴𝐵
Endpoint Reaction:
𝐼𝑛 + 𝐵 → 𝐼𝑛𝐵
In B – with significant difference in appearance in solution than
In at end point; color change
Types of Argentometric titrations:
1. The Mohr Method – formation of a 2nd precipitate) –
widely applied for the titration of Cl, Br, or Cn with
standard AgNO3
Indicator Na2CrO4
Titration Reaction: (White Precipitate)
𝐴𝑔m + 𝐶𝑙 n ↔ 𝐴𝑔𝐶𝑙(()

Endpoint Reaction: (Red Precipitate)

2𝐴𝑔m + 𝐶𝑟𝑂ƒ }n ↔ 𝐴𝑔2𝐶𝑟𝑂ƒ (()

Ksp AgCl = 1.8 x 10-10

Ksp Ag2CrO4 = 1.2 x 10-12
Mohr Titration at pH 7-10; pH < 7 [CrO42-] protonates; pH >10
Ag2O precipitates
Solubility – Ag2CrO4 is more soluble than AgCl so all x-
precipitate as Ag2CrO4 with correct pH
2. Volhard Method – formation of a colored complex;
Ag+ titrated with standard KSCN; titration in acidic
solution to prevent precipitation of Fe3+ as hydrated
oxide; most important application – indirect
determination of X-( add excess Ag+ and back titration
with standard SCN-)
Titration Reaction:
𝐴𝑔m + 𝑆𝐶𝑁 n ↔ 𝐴𝑔𝑆𝐶𝑁(()

Endpoint Reaction: (blood red complex wherein Fe2+ is the

indicator)
𝐹𝑒 }m + 𝑆𝐶𝑁 n ↔ 𝐹𝑒𝑆𝐶𝑁 }m
 COMPLEX FORMATION TITRATION/ COMPLEXOMETRIC [𝑀𝑌 (2nƒ) ]
TITRATION: [𝑀2m ]} =
𝐾′¢Ž
Coordination Compounds/ Complexes – formed by the Cations with larger Kf provide good end points even in acidic
reaction of a metal ion with ligands via a Lewis Acid and Base solutions Fe3+ and In3+ can be ti trated even at strongly acidic
Reaction wherein the metal acts as the Lewis Acid (e- pair solutions (pH = 2)
acceptor) and the ligands act as the Lewis Base (e- pair donor)
Ca2+, Zn2+, Al3+. Fe2+ in moderately acidic pH only
Chelate – complex produced when metal ions coordinates with
2 or more donor groups of a single ligand to form a Auxillary Complexing Agent – sometimes added to keep metal
heterocyclic ring ion in the solution at pH required for the titration; decreases the
sharpness of the endpoints e.g. Zn2+ titration in NH3-NH4Cl
EDTA – hexadentate ligand with 6 donor atoms (2N and 4O) buffer – NH3 prevents formation of Zn(OH)2 by forming NH3
with 4 acidic Hs with 4 Kas complexes with the Zn2+
Total Molar Concentration of Uncomplexed EDTA Titration Reaction:
𝐶ž = [𝑌 ƒn ] + [𝐻𝑌 •n ] + [𝐻} 𝑌 }n ] + [𝐻• 𝑌 n ] + [𝐻ƒ 𝑌] 𝑍𝑛(𝑁𝐻• )}m •n
→ 𝑍𝑛𝑌 }n + 3𝑁𝐻• + 𝑁𝐻ƒ m
ƒ + 𝐻𝑌
[𝐻ƒ 𝑌] [𝐻• 𝑌 n ] [𝐻} 𝑌 }n ] Metallochromic Indicators – colored organic compounds (dyes)
𝛼 = 𝛼‚ = 𝛼} =
𝐶ž 𝐶ž 𝐶ž that form colored chelates with metal ions; chelates of different
color for free indicator; widely used Eriochrome Black T (EBT)
[𝐻𝑌 •n ] [𝑌 ƒn ]
𝛼• = 𝛼ƒ =
𝐶ž 𝐶ž 𝐻} 𝐼𝑛 n (𝑟𝑒𝑑) + 𝐻} 𝑂 ↔ 𝐻𝐼𝑛}n (𝑏𝑙𝑢𝑒) + 𝐻• 𝑂m

Plot of á values vs. pH; 𝐻𝐼𝑛}n (𝑏𝑙𝑢𝑒) + 𝐻} 𝑂 ↔ 𝐼𝑛•n (𝑜𝑟𝑎𝑛𝑔𝑒) + 𝐻• 𝑂m

K’ - conditional & effective formation constant (pH dependent At pH >7, blue HIn2- predominate if there are no metal ions
Keq, applicable at a single pH only); used to calculate the
Endpoint Reaction:
equilibrium concentration of a metal ion and complex at any
point in the titration curve 𝑀𝐼𝑛n (𝑟𝑒𝑑) + 𝐻𝑌 •n ↔ 𝐻𝐼𝑛}n (𝑏𝑙𝑢𝑒) + 𝑀𝑌 }n
𝑀2m + 𝑌 ƒn ↔ 𝑀𝑌 (2nƒ) Kf metal-indicator <.1
[𝑀𝑌 (2nƒ) ] Kf metal-EDTA Complex otherwise premature endpoint is observed
𝐾¢Ž = 𝐾'W( = 2m ƒn
[𝑀 ][𝑌 ] Titration Methods Employing EDTA:
(2nƒ)
[𝑀𝑌 ] 1. Direct
𝐾′¢Ž = 2m
= 𝛼ƒ 𝐾¢Ž
[𝑀 ]𝐶ž 2. Back
3. Displacement
EDTA Titration:
Determination of Water Hardness – determination of water
pM vs V EDTA
quality through the titration of EDTA
1. Initial pM (V EDTA = 0ml) : pM = -log [Mn+]
Hardness – total concentration of alkaline earth ions in water
2. Preequivalence Point (V EDTA = xml)
𝑚𝑜𝑙𝑠¢ − 𝑚𝑜𝑙𝑠£Šže [Ca2+] & [Mg2+] > concentration of other alkaline earth ions
𝑝𝑀 = − 𝑙𝑜𝑔 𝑙𝑜𝑔
𝑉ž1;'9
Hardness = [Ca2+] + [Mg2+] expressed in CaCO3/Li
3. Equivalence Point (V EDTA = yml)
𝑚𝑜𝑙𝑠¢ Water Hardness Category CaCO3/Li
¤𝑀𝑌 (2nƒ) ¥ = Soft <17.1
𝑉+f:-9.
Moderately Soft 17.1-60
[𝑀2m ] = 𝐶ž Moderately Hard 60-120
Hard 120-180
[𝑀𝑌 (2nƒ) ] Very Hard >180
𝐾′¢Ž = Liebig Titration – titration involving unidentate ligand; endpoint
[𝑀2m ]𝐶ž
is marked by appearance of turbidity (precipitation of AgCN)
[𝑀𝑌 (2nƒ) ]
[𝑀2m ]} = 𝐴𝑔m + 2𝐶𝑁 n ↔ 𝐴𝑔(𝐶𝑁)} n
𝐾′¢Ž
4. Post Equivalence Point (with excess EDTA) 𝐴𝑔m + 𝐴𝑔(𝐶𝑁)} n ↔ 𝐴𝑔m [𝐴𝑔(𝐶𝑁)} ] 𝑜𝑟 𝐴𝑔𝐶𝑁
𝑚𝑜𝑙𝑠¢ Deniyes Modification:
¤𝑀𝑌 (2nƒ) ¥ =
𝑉;1;'9
𝐾𝐼 + 𝑁𝐻• → 𝐴𝑔𝐼 (𝑝𝑎𝑙𝑒 𝑦𝑒𝑙𝑙𝑜𝑤)
𝑚𝑜𝑙𝑠£Šže − 𝑚𝑜𝑙𝑠¢
[𝑌 ƒn ] = 𝐶ž = Generalized Equation for Redox Reaction:
𝑉ž1;'9

[𝑀𝑌 (2nƒ) ] 𝐴*+/ + 𝐵13 ↔ 𝐴13 + 𝐵*+/

𝐾′¢Ž =
[𝑀2m ]𝐶ž Red: 𝐵13 + 𝑛𝑒 n ↔ 𝐵*+/
Ox: 𝐴*+/ ↔ 𝐴13 + 𝑛𝑒 n Sign of the electrode potential indicates whether the reaction is
spontaneous
Redox Reactions are typically carried out in an electrochemical
cell in which the reactants (OA and RA) are not in direct Nernst Equation:
contact with one another; connected via salt bridge
𝑅𝑇 𝑎‰, 𝑎Š/ …
Electrochemical Cell – 2 conductors (electrodes) each of which 𝐸 = 𝐸° − 𝑙𝑛 𝑙𝑛 ' W
𝑛𝐹 𝑎e 𝑎€ …
is immersed in an electrolyte solution
0.0592 𝑎‰, 𝑎Š/ …
Cathode – electrode where reduction occurs 𝐸 = 𝐸° − 𝑙𝑜𝑔 𝑙𝑜𝑔 ' W
𝑛 𝑎e 𝑎€ …
Anode – electrode where oxidation occurs
If x = solute, ax ~ [x]
Electrodes – can be metal electrodes directly involved in the
reaction or an inert electrode like Pt If x = gas, ax ~ Px, atm

Cathodic Reaction when there is no easily reduced species: If x = pure liquid, solvent or solid, ax ~ 1
Formal Potential – electrode potential when analytical
2𝐻 m + 2𝑒 n ↔ 𝐻}(K)
concentrations are used in the place of molar concentrations
Anodic Reaction when there is no easily oxidized species:
Thermodynamic Potential of an Electrochemical Cell (Ecell):
m n
2𝐻} 𝑂 ↔ 𝑂}(K) + 4𝐻 + 4𝑒
𝐸,+99 = 𝐸,';k1/+ − 𝐸'21/+
Types of Electrochemical Cells: Calculation of Redox Equilibrium Constants from Standard
Galvanic or Voltaic Cells – with spontaneous redox reaction Potentials:

Electrolytic Cell – with nonspontaneous redox reaction and 𝐵13 + 𝑏𝑒 n ↔ 𝐵*+/

requires an external source of electrical energy for operation 𝐴13 + 𝑎𝑒 n ↔ 𝐴*+/
Schematic Representation of Cells:
Cathode: 𝑎𝐵13 + 𝑎𝑒 n ↔ 𝑎𝐵*+/
Anode | Electrolyte Solution of Anode || Electrolyte Solution of
Anode: 𝑏𝐴*+/ ↔ 𝑏𝐴13 + 𝑏𝑒 n
Cathode | Cathode
Balanced Reaction: 𝑏𝐴*+/ + 𝑎𝐵13 ↔ 𝑏𝐴13 + 𝑎𝐵*+/
Electrons from the anode to the cathode
At equilibrium ÄG = 0, ÄG = -nFE
If some cell is connected to a battery, the electron flow is
reversed thus producing an electrolytic cell 𝐸,+99 = 0 = 𝐸,';k1/+ − 𝐸'21/+
Reversible Cell – in which the direction of the electrochemical 𝐸,';k1/+ = 𝐸'21/+
reaction is reversed when the direction of the current (electron
flow is reversed) 0.0592 0.0592 [𝐴*+/ ]W
𝐸°€ − = 𝐸°e − 𝑙𝑜𝑔 𝑙𝑜𝑔
𝑎𝑏 𝑎𝑏 [𝐴13 ]W
Irreversible Cell – cell wherein the reversing of the current
causes an entirely different half-reaction to occur at either one 0.0592 0.0592
𝐸°€ −𝐸°e = = 𝑙𝑜𝑔 𝑙𝑜𝑔 𝐾+f
or both the electrodes 𝑎𝑏 𝑎𝑏
Electrode potential – measure of the tendency for the reaction 𝑎𝑏(𝐸°€ −𝐸°e )
𝑙𝑜𝑔 𝑙𝑜𝑔 𝐾+f =
to proceed from a nonequilibrium state to equilibrium. 0.0592

∆𝐺 = −𝑛𝐹𝐸°,+99 = −𝑅𝑇 𝑙𝑛 𝑙𝑛 𝐾+f Redox Titration Curve: electrode potential for the redox system
vs. VTitrant
Cell Potential:
Indicators Used: OA or RA that responds to the change in
Saturated Calomel Electrode – ESCE = 0.244V potential of the system rather than changes in concentration of
n any particular product or reactant
𝐻𝑔} 𝐶𝑙} + 2𝑒 n ↔ 2𝐻𝑔(9) + 2𝐶𝑙 ('f)
Electrode Potential System – equilibrium attained after each
Standard Hydrogen Electrode (SHE) – basis of oxidation- addition of titrant; system at equilibrium at all times throughout
reduction potentials E° = 0.00V the titration
2𝐻 m + 2𝑒 n ↔ 𝐻}(K) Example:
Strongest Reducing Element – Li metal 𝐶𝑒 ƒm + 𝐹𝑒 }m ↔ 𝐶𝑒 •m + 𝐹𝑒 •m
Strongest Oxidizing Element – Fluorine 𝐸(y(;+= = 𝐸‰+ ¬• − 𝐸j+ -•
IUPAC Convention – electronic potential is reversed If indicator is present: (concentrations vary as titration
exclusively for half-reactions written as reductions proceeds; Esystem varies as well)𝐸š2 = 𝐸(y(;+= = 𝐸‰+ ¬• −
Reverse reactions are spontaneous when standard state 𝐸j+ -•
conditions apply
Hypothetical Cell of the Titration Mixture:
SHE||Ce4+,Ce3+,Fe3+, Fe2+|Pt Ce4+ Ce3- 1.44 Na2C2O4, Fe,
As2O3,
Apply Nernst Equation: K2Cr2O7 Cr 3+ 1.33 K2Cr2O7, Fe
1. Before equivalence point: 𝐸‰+ ¬• I2 I- 0.536 BaS2O3∙H2O,
Na2S2O3
2. Equivalence Point: 𝐸‰+ ¬• & 𝐸j+ -•
KMnO4 – most widely used of all standard oxidizing agents;
3. After Equivalence Point: 𝐸j+ -•
readily available; inexpensive, requires no indicator
Effect of Completeness of Reaction in Redox Titration Curves:
𝑀𝑛𝑂ƒn + 8𝐻 m + 5𝑒 n ↔ 𝑀𝑛}m + 4𝐻} 𝑂 E° = 1.51V
The larger the Keq, the larger the ÄE at the equivalence point
In Acidic Solution: 𝐻} 𝐶} 𝑂ƒ ↔ 2𝐶𝑂} + 2𝐻 m + 2𝑒 n E° =
region
0.48V
Effect of Concentration of redox Titration Curves:
Reaction with KMnO4:
Titration Curves are independent of concentration of reactants
2𝑀𝑛𝑂ƒn + 5𝐻} 𝐶} 𝑂ƒ + 6𝐻 m + 5𝑒 n ↔ 2𝑀𝑛}m +
and are independent of dilution over a considerable range
10𝐶𝑂} + 8𝐻} 𝑂
Types of Redox Indicators:
Ce4+ in H2SO4 – powerful oxidizing agent; yellow-orange;
1. General Redox Indicators – respond to the potential stoichiometry of reaction is simple; indefinitely stable but
of a system; substance that changes color upon being relatively high cost of Ce4+ compounds; indicator ferroin
oxidized or reduced; change in color depends only
upon potential of the system I2 – solutions are weak oxidizing agents; used for the
determination of strong reductants; lack stability; must be
𝐼𝑛13 ↔ 𝐼𝑛*+/
restandardized regularly; I2 is not very soluble in water;
0.0592 [𝐼𝑛*+/ ] dissolved moderately in concentrated KI
𝐸 = 𝐸°š2 − 𝑙𝑜𝑔 𝑙𝑜𝑔
𝑛 [𝐼𝑛13 ]
𝐼•n + 2𝑒 n ↔ 3𝐼 n
Color change occurs when there is a change in the ratio of the
Iodimetry – I2 used as OA
reactants of about 100
[𝐼𝑛*+/ ] 1 [𝐼𝑛*+/ ] Iodometry – I2 used as RA; standard Na2S2O3 used to titrate I2
< 𝑐ℎ𝑎𝑛𝑔𝑒𝑠 𝑡𝑜 ≥ 10
[𝐼𝑛13 ] 10 [𝐼𝑛13 ] liberated by reaction of analyte in measured excess KI in
slightly acidic solution
Full color change when
0.0592 𝐼} + 2𝑆} 𝑂• }n ↔ 2𝐼n + 𝑆ƒ 𝑂Y }n
𝐸 = 𝐸°š2 ±
𝑛
𝐼𝑂•n + 5𝐼 n + 6𝐻 m ↔ 3𝐼} + 3𝐻} 𝑂
Choose indicator which would change color near the
equivalence point 3𝐼} + 6𝑒 n ↔ 6𝐼 n
e.g Ferroin (Phen)3Fe2+
1 𝑚𝑜𝑙 𝐼𝑂•n ≡ 3 𝑚𝑜𝑙𝑠 𝐼} ≡ 6 𝑚𝑜𝑙𝑠 𝑆} 𝑂• }n
𝑃ℎ• 𝐹𝑒 •m + 𝑒 n ↔ 𝑃ℎ• 𝐹𝑒 }m
𝐹𝑊µš—-
𝐹𝑒𝑟𝑟𝑖𝑖𝑛 (𝑏𝑙𝑢𝑒)(𝑜𝑥) ↔ 𝐹𝑒𝑟𝑟𝑜𝑖𝑛(𝑟𝑒𝑑)(𝑟𝑒𝑑) 𝐸𝑊µš—- =
6
2. Specific Indicator – reacts in a specific manner with Indicator: Starch (specific indicator) – deep blue complex with
one of the reactants in titration to produce a color e.g. I2
Starch forms a dark blue complex with I3- which is the
end point of titrations with I2 or KSCN (blood red Standard Reductants – standard solutions of reducing agents
complex) tend to react with atomic O2; titrations carried out in reagents
Iodometry – indirect; I3- is more soluble and it keeps the I2 in under an inert atom; Indirect method used – aliquot containing
the solution excess reductant added to the sample and the excess is
Iodimetry – direct quickly back titrated with standard oxidant

Redox Titration: Reagent Oxidatio 1° Stability of

n Standar Solution
Redox Titration – widely used in titrimetric analysis; analyte Potential d
can be present in the sample in more than 1 oxidation state Fe (II) -0.77 K2Cr2O7, Unstable unless
and must be converted to a single oxidation state prior to its 𝐹𝑒 }m Fe protected form
titration; auxillary OA (e.g. H2O2) or RA (Zn, Cd, Hg) may be → 𝐹𝑒 •m + 𝑒 n O2
added to accomplish this Na2S2O3 0.08 KIO3, I2 Frequent
}n standardization
Standard Oxidants: 2𝑆} 𝑂•
→ 𝑆ƒ 𝑂Y }n required
Reagent Reduction Standard 1° Standard + 2𝑒 n
Product Potential (V) Used As(III) -0.56 AsO3, I2 Indefinitely
KMnO4 Mn2+ 1.51 Na2C2O4, Fe, 𝐻• 𝐴𝑠𝑂• stable if acidic
As2O3 + 𝐻} 𝑂
KBrO3 Br- 1.44 KBrO3 → 𝐻• 𝐴𝑠𝑂ƒ
+ 2𝑒 n
Na2S2O3 – moderately strongreducing agent, widely used to
determine oxidizing agents by indirect procedure that involves
I2 as an intermediate
 Potentiometry:
Potentiometry – a simple, easy to use and inexpensive
electroanalytical technique based upon potential
measurements; makes use of a pH meter; involves
measurements of potential difference between a pair of
suitable electrodes immersed in a solution to be analyzed
Potentiometric Methods:
Reference Electrode (Eref) | Salt bridge (Ej) | Analyte Solution |
Indicator Electrode (Eind)
𝐸,+99 = 𝐸-2/ − 𝐸*+l + 𝐸¶ 8. Solid State Membrane Electrode – consists of an insoluble
Junction Potential – potential that develops across an interface
between 2 solutions that differ in their electrolyte solution;
junction potential at 2 ends of a salt bridge tend to cancel each
other
Reference Electrodes – half-cells which have a constant
potential and are completely insensitive or independent of
composition of the analyte solution
Indicator/Sensing Electrode – electrode having potential that is
dependent on analyte solution; should respond rapidly and
selectively to anaylte of interest; should have reproducible
response; there is no indicator electrode that is absolutely
specific in its response
Types of Indicator Electrodes:
1. Standard Hydrogen Electrode (SHE) – troublesome to
maintain & use
2. Calomel RE – Hg | Ag2Cl2 (satd.), KCl (xM) x = 0.11M and
satd. ~ 4.6M
ESCE = 0.244V
n
𝐻𝑔} 𝐶𝑙} + 2𝑒 n ↔ 2𝐻𝑔(9) + 2𝐶𝑙 ('f) 1. Gas Sensing Probe – responds to specific gases
3. Ag/AgCl RE – Ag | AgCl (satd), KCl (satd.)
EAg/AgCl = 0.199V
n n
𝐴𝑔𝐶𝑙(() + 𝑒 n ↔ 𝐴𝑔(() + 𝐶𝑙('f) surrounded by a gas-permeable membrane
4. Metallic Indicator Electrodes of the 1st Kind – simplest;
usually constructed from coils of metal wire or flat metal
plates e.g. Ag and Cu wires
Pure Metal Electrodes in equilibrium with its cation solution
𝑋 2m + 𝑛𝑒 n ↔ 𝑋(() Most popular is the Urea Electrode – urease hydrolyses urea
During potentiometric measurement, potential of RE remains
constant while potential of indicator electrode is proportional to
activity of analyte as described by the Nernst Equation (valid
only when essentially no current flows through the cell)
1st Order Metallic Electrode – responds to its cation
2nd Order Metallic Electrode – responds to its anion that forms
a sparingly soluble precipitate or stable complex with their
cation
5. Inert Metallic Electrode – inert metallic electrode for redox
systems e.g. Pt, Au or C; responds to potential of the
redox system with which it is in contact
6. Membrane Electrodes – p Ion electrode employing a
selective membrane as a sensing element; most are Ion
selective electrodes and exhibit good selectivity or specific
ions based on measurement of potential generated across
a membrane; selective membrane usually attached to the
ed of a tube that contains an internal RE
7. Glass Electrodes – 1st membrane electrode developed
and still the most widely employed glass membrane
electrode for pH measurements; pH sensitive part is a thin
glass blub at the bottom of the electrode
Glass Membrane Composition (Corning 015 Glass): 22% Na2O. 6%
CaO, 72% SiO2 (specific for H+ up to pH 9); can respond
to cations like Na+ and K+ at higher pH
Boundary Potential – basis for pH Measurement
salt/crystal; difference is membrane at the bottom; e.g.
Fluoride Electrode – the sensing element is a single
crystal of lanthanum fluoride, LaF3, alongside Europium
Fluoride, EuF2 to create lattice vacancies. Such a crystal
is an ionic conductor by virtue of the nobility of fluoride
9. Liquid Membrane Electrode
10. Hydrophobic Polymer membrane – saturated liquid ion
exchanger
Ionophores – metal macrocyclic ion carrier dissolved in a
viscous organic membrane; liquid ion exchanger; interacts with
a pH meter via its internal reference cell; enables the ion of
interest to penetrate the membrane
Direct indicator – species selective
Indirect indicator – ion specific electrodes that react with other
compounds
Molecular Selective Electrodes – 2 membranes are used to
generate response ad each membrane and each has its own
selectivity characteristics
2 Types of MSE:
dissolved in solutions; P inside the probe, inert
sensing element glass electrode; other ion selective
electrode surrounded by an electrolyte solution
2. Enzyme Electrodes – constructed by covering a
surface of MSE with the enzyme immobilized in some
matrix. The immobilized enzyme catalyzes the
production of an ion that is detected by the electrode
response is proportional to the substrate; used for
diabetes; analyzes glucose using glucose oxidase
and forms ammonia and changes pH; Urea is the first
compound synthesized; cellophane wrapped around
the pH electrode
Combination Electrode – both indicator and reference in the
same body
Instruments for Measuring Cell Potentials with High Resistance
(R Internal = 1011 to 1012 Ù)
Direct reading digital Voltmeter – pH meters/ p Ion meter; ion
meters
Direct Potentiometric Measurements – rapid and convenient
method for determining activity of diferrent cations and anions;
need standard solutions of known analyte ; needs calibration
curve
Conversion in Potentiometry – indicator electrode always Plot of ÄE/ÄV vs. V Titrant -
treated as cathode; RE as anode
Plot of Ä2E/ÄV2 vs. V Titrant -
𝐸,+99 = 𝐸-2/ − 𝐸*+l + 𝐸¶
Graphical determination of endpoint – valid if titration curve
For Cations: symmetrical about equivalence point and inflection curve
corresponds to this point; analyte and titrant react in equimolar
0.0592
𝐸,+99 = 𝑘 − 𝑝𝑋 ratio
𝑛
𝐸,+99 − 𝑘
𝑝𝑋 = −
0.0592/𝑛
For Anions:
0.0592
𝐸,+99 = 𝑘 + 𝑝𝐴
𝑛
𝐸,+99 − 𝑘
𝑝𝐴 =
0.0592/𝑛
Nikolsky Equation:

zº
𝑅𝑇 z»
𝐸 = 𝐸° − 𝑙𝑛 𝑙𝑛 [𝑎- + ‡ (𝑘- 𝑗𝑎¶ ) ]
𝑧- 𝐹

Nerntian Slope and Selectivity – test for electrodes

Potentiometric measurements in terms of concentration;
results differ if the activity used high ionic strength in the
unknown sample
Total Ionic Strength Adjustment Buffer (TISAB) – used to
watch the ionic strength of the analyte solution and that of the
standards (inert electrolyte)
Operational Definition of pH (by NIST and IUPAC) – based on
direct calibration of pH meter with standard buffer followed by
determination of pH of unknown solution
𝐸( − 𝑘
𝑝𝐻 𝑠 =
0.0592
𝐸: − 𝑘
𝑝𝐻 𝑢 = −
0.0592
(𝐸: − 𝐸( )
𝑝𝐻 𝑢 = 𝑝𝐻 𝑠 −
0.0592
Exact pH:
𝑝𝐻 = 𝑙𝑜𝑔 𝑙𝑜𝑔 (𝛾• • + [𝐻 m ] )
NOISE reacts to one specific compound
Selectivity Coefficient, Kij – measure of extent of interference of
a particular ion of a given electrode response; ideally 0 and the
more selective it is, the closer it is to 0
aj = interfering ion activity
zj = charge of interfering ion
Potentiometric Titration – titrations wherein the potential of a
suitable electrode is measured as a function of the titrant
solution; readily automated by autotitrators; usual
potentiometric set-up but add burette with titrant; Ecell
measured and recorded after each addition of titrant
End Point Detection:
Direct plot of E vs. V titrant – sigmoidal
Spectrophotometry: Spectrophotometer – instrument for measuring transmittance
or absorbance of a sample as a function of λ or at a single λ;
Absorption Spectroscopy:
may be manual (single beam) or recording (double beam)
b Basic Components:

P0 1. Light Source
Absorbing P
Sol’n with 2. Wavelength Selector
Conc. C 3. Sample
4. Detector
5. Signal Processor and Readout

Attenuation of a Beam of Radiation by an Absorbing Solution Region λ

UV 180-380 nm
Power of the beam decreases from P0 to P (decrease of Visible 380-780 nm
radiant power) Near – IR 0.78 – 2.5 ìm
Mid – IR 2.5 -50 ìm
P0 – incident radiant power
Best Light Source for UV – H2 & D2 Lamps
P – transmitted radiant power
Best Light Source for Visible Light – Tungsten Lamps
Transmittance, T of solution - fraction of incident radiation
Limitations of Beer’s Law:
transmitted by the solution (often expressed as %T)
1. only monochromatic light at a single wavelength
Absorbance, A of a solution:
2. accounted only in relatively concentrated solutions
𝑃 𝑃(19.+2; (usually >0.01M)
𝐴 = − 𝑙𝑜𝑔 𝑙𝑜𝑔 𝑇 = 𝑙𝑜𝑔 𝑙𝑜𝑔 = 𝑙𝑜𝑔 𝑙𝑜𝑔 3. apparent chemical derivations – when analyte dissociates,
𝑃 𝑃(19:;-12
associates or reacts with a solvent to generate a product
Bouger’s or Lambert’s Law – transmitted radiant power with a different absorption
decreases exponentially as path length increases
Most common monochromators – gratings (prisms can also be
𝑑𝑃 𝑑𝑃 used but not often)
= 𝐾‚ 𝑃 − = 𝐾‚ 𝑑𝑏
𝑑𝑏 𝑃
Sample Container – fused silica or quartz
½ W
𝑑𝑃
−¼ = 𝐾‚ ¼ 𝑑𝑏 Detector – transducer (converts one form of signal into
½¾ 𝑃
another) that converts radiant energy into electrical signal;
𝑃 𝑃 photon detectors like phototubes
𝑙𝑛 𝑙𝑛 = 𝐾‚ 𝑏 𝑙𝑜𝑔 𝑙𝑜𝑔 = 𝐾} 𝑏 𝐾} = 𝑒𝐾‚
𝑃 𝑃
Read-Out Device – meter or recorder
Beer’s Law – the transmitted radiant power decreases
exponentially as concentration increases (strictly applicable Monochromatic light – same density – equitransparent
only for monochromatic radiation) cuvettes

Combined Bouger-Beer’s Law or simply Beer’s Law: Master grate – diamond cutter; evenly distributes grooves for
grating
𝑃
𝑙𝑜𝑔 𝑙𝑜𝑔 = 𝐾 𝑏𝐶 Grating rotates – angle changes the λ passing through
𝑃
𝐴 = 𝛼𝑏𝐶 𝐴 = 𝜀𝑏𝐶 𝜀 = 𝛼 𝑥 𝑀𝑊 Photosensitive surface turns into photon detectors – electrons
will be emitted. If the electron flows, current is developed. The
𝑃 𝑃 current is converted into voltage since voltage is easily
𝑇 = %𝑇 = 𝑥 100%
𝑃 𝑃 increased
Application of Beer’s Law to Mixtures: 𝑖 = 𝑘𝑉
Beer’s Law is applicable also to solutions containing more than Standard Addition Method - to minimize effects of sample
one kind of absorbing substances provided there is no matrix; add one or more increments of standard solution to
interaction that occurs among the various species; total A for sample aliquots of same size with the same final volume
the multicomponent system is the sum of individual As
Analyte/Sample (Vx = aliquot, VT = total volume)
𝐴 ž1;'9 = 𝐴‚ + 𝐴} + 𝐴• + ⋯ + 𝐴2
𝜀W 𝑉3 𝐶3
𝐴 ž1;'9 = 𝜀‚ 𝑏𝐶‚ + 𝜀} 𝑏𝐶} + 𝜀• 𝑏𝐶• + ⋯ + 𝜀2 𝑏𝐶2 𝐴‚ =
𝑉ž
Spectroscopic Method for Chemical Analysis – non- Analyte + Standard:
stoichiometric; need a calibration curve
𝜀W 𝑉3 𝐶3 𝜀W 𝑉( 𝐶(
𝐴} = +
𝑉ž 𝑉ž
Instrumentation: Concentration of Sample:
 𝐴‚ 𝐶( 𝑉(
𝐶L =
(𝐴} − 𝐴‚ )𝑉3
If weak acid, control pH with a buffer in order to make one form
predominate by controlling pH