Session 2:

Fundamentals and
Classical methods of quantitative
elemental analysis

http://bcs.whfreeman.com/qca7e
http://www.good-weighing-practice.com/gwp/proper-weighing
Measurement of Mass and
Volume:

Recognising random and

systematic errors
 Recap:
Quantitative Analysis - Principles
1) Define sample amount (mass or volume)
2) Measure quantity proportional to analyte
concentration
 Measured property must vary in a defined way:
calibration with known standards necessary
 Analysis must be specific: Interferences must
be known and if possible be eliminated
 Accuracy: Proximity of measured value to accepted
(or "true") value: must be determined
 Precision: Closeness of measured values to one
another: must be defined and reported
 Measuring Mass

Classical two-pan balance Modern electronic

analytical balance

F=mxg

Electroma-
gnetic force
From: Harris, 6th edition to counter
 Random errors in weight
measurements:
tolerances of analytical balances and
weights for calibration
 Analytical balances need to be calibrated regularly
 Typically use stainless steel weights (d = 8.0 g/ml)

From: Harris, 6th edition

 Specifications for balances

 Capacity
 Readability
 Repeatability (standard deviation); larger
than readability

Capacity x readability:

Analytical balances: tens to hundreds of g x 0.1 - 0.01 mg

Ultra-micro balance: e.g. 6 g x 0.0001 mg
 Avoiding systematic error in
weight measurements:
buoyancy
 Any object displaces a certain amount of air
 This reduces the apparent mass that a balance measures
 If density of the object being weighed is significantly
different from calibration weights, buoyancy correction
is necessary:
 da 
m' 1  
m  dw 
 da 
1  
 d 

m = true mass; m’ = measured mass; da = density of air (0.0012 g/ml); dw =

density of calibration weights (8.0 g/ml); d = density of weighed object
 Correcting buoyancy errors

Buoyancy correction in dependence on density of weighed object

 Exercise:
 A bottle weighed 7.6500 g empty and 9.9700 g after introduction
of an organic liquid with a density of 0.92 g cm-3. The balance
was equipped with stainless steel weights having a density of 8.0
g cm-3. Correct the weight of the sample for the effects of
buoyancy.
 Avoiding systematic errors in
weight measurements
 Temperature effects
 Convection air currents
 Warm air in balance weighs less
 Measured mass of object appears lower
 Essential to weigh at room temperature
 Prevent object from picking up moisture: Absolute error in weight
 Do not touch with bare fingers as a function of time
 Let cool in desiccator after object was
removed from a 110°C
 If weighing substances that are kept in oven (A: porcelain
fridge or freezer, let warm up before weighing filtering crucible, B:
 Be aware of hygroscopic substances weighing bottle
containing 7.5 g of KCl.)
 Measuring Volume
 Apparatus for volume measurement
 Pipettes, Burettes, Volumetric flasks

Calibrated either for

Typical pipettes: (a) volumetric (transfer containment (flasks) or delivery
pipette); (b) Mohr; (c) serological; (d) (pipettes, burettes) of specified
Eppendorf micropipette volume
 Characteristics of pipettes

Name Function Capacity Type of

(cm3) drainage
Volumetric Delivery of fixed volume 1-200 Free
Mohr Delivery of variable volume 1-25 To lower
calibration line
Serological Delivery of variable volume 0.1-10 Blow out last
drop
Eppendorf Delivery of fixed or variable 0.001-1 Empty tip by air
vol. displacement
 Random errors in volume
measurements:
Tolerances of Class A Pipettes
Capacity (cm3) Tolerances (cm3)
0.5  0.006
1  0.006
2  0.006
5  0.01
10  0.02
20  0.03
25  0.03
50  0.05
100  0.08
 Random errors in volume measurement:
Range and precision of typical Eppendorf micropipettes

Volume range (mL) Standard dev. (mL)

1-20 <0.04 @ 2 mL
<0.06 @ 20 mL
10-100 <0.1 @ 15 mL
<0.15 @ 100 mL
20-200 <0.15 @ 25 mL
<0.3 @ 200 mL
100-1000 <0.6 @ 250 mL
<1.3 @ 1000 mL
500-5000 <3 @ 1000 mL
<8 @ 5000 mL
 Tolerances of Class A burettes and
volumetric flasks
Burette Vol. Tolerance (mL) Volumetric Tolerance (mL)
(mL) flask vol. (mL)
5  0.01 5  0.02
10  0.02 10  0.02
25  0.03 25  0.03
50  0.05 50  0.05
100  0.20 100  0.08
250  0.12
500  0.20
1000  0.30
2000  0.50
 Avoiding systematic errors in
volume measurements:
Temperature effects
 Volume occupied by a given mass of liquid, as well
as the device that holds the liquid, varies with
temperature
 For dilute aqueous solution:
 Coefficient of expansion = 0.025% / °C
 1°C increase in temp. yields 0.025% increase in volume.
 Refer volumetric measurements to temperature at which
they were made (standard temperature is 20 °C).

Exercise:
A 40.00 mL sample is taken from an aqueous solution at 5°C.
What volume does it occupy at 20 °C?
 Avoiding systematic errors in
volume measurement:
Calibration of Volumetric Ware
 Measure mass of liquid of known density and
temperature contained in or delivered by a stated
volume
 Buoyancy correction must be made (see Table)
 Divide corrected mass by density of liquid
 Express results at standard temperature (20°C).
Volume occupied by 1.0000g water weighed in
air against stainless steel weights
Volume (mL/g) at T
Temperature T (°C) Corrected for Corrected for buoyancy and
buoyancy change in container volume
= volume @ 20°C
10 1.0013 1.0016
12 1.0015 1.0017
14 1.0018 1.0019
16 1.0021 1.0022
18 1.0024 1.0025
20 1.0028 1.0028
22 1.0033 1.0032
25 1.0040 1.0036
26 1.0043 1.0041
28 1.0048 1.0046
30 1.0054 1.0052
Exercise:
A 25 mL pipette has been measured to deliver 24.976 g of water weighed
against stainless steel mass at 25°C. Use the data in the Table to
determine the volume delivered by this pipette at 25°C and 20 °C.
 Treatment of glassware

 Need to ensure that containers are clean

and not contaminated
 Important that liquids interact in defined
way with glass surfaces: use detergents
 For trace analysis, it is common to use an
“acid wash”
 If possible, use polypropylene or teflon
rather than glass
 Summary
 All measurements carry errors/uncertainty
 Systematic errors can be corrected
 Accuracy of methods can be improved
 Random errors cannot be corrected
 Precision of method can be determined and must be
known
 All quantitative data must be reported with
error
 Methods to solve a given analytical question
can be selected according to their performance
characteristics
 Analysts must be aware of the
performance characteristics of their tools
Classical analytical methods:

Gravimetric and volumetric

analyses
 Gravimetric analysis
 Analyte is converted to a solid product of known
(pure) composition and weighed
 Conversion of the analyte can be accomplished in
several ways:
 Reduction of an ion to its elemental form (e.g. by
electrolysis)
 Roasting (hydrolysis/oxidation) of a compound
 Precipitation of an ion with a counterion
 Precipitation of an organic molecule
 Methods exist for most inorganic anions and
cations, H2O, SO2, CO2, and iodine
 Organic compounds can also be quantified
 Examples
 Convert analyte (usually ions) to its elemental form using reducing agents
Reducing agent Analyte
SO2 Se, Au
SO2 + H2NOH Te
H2NOH Se
H2C2O4 Au
H2 Re, Ir
HCOOH Pt
NaNO2 Au
SnCl2 Hg

 Precipitate analyte using precipitating agent

Precipitating agent Ion precipitated (Precipitate)
AgNO3 Cl- (AgCl), Br- (AgBr), I- (AgI)
HCl Ag+ (AgCl), Hg+ (Hg2Cl2),
Na+ (NaCl)
HNO3 Sn4+ (SnO2)
H2SO4 Li+, Mn2+, Sr2+, Cd2+, Pb2+, Ba2+ (all as sulfates)

H2C2O4 (oxalate) Ca2+, Sr2+, Th4+ (as oxalates or oxides)

 Gravimetric analysis: precipitation
of insoluble salts or complexes
 Involves precipitation, filtration, drying,
weighing
 e.g.: Sulfate with BaCl2
 Ni(II) with dimethylglyoxime
 8-hydroxyquinoline (oxine): range of metal ions.
Forms sparingly soluble complexes

 For accuracy, certain conditions must be fulfilled:

 The ion of interest must precipitate completely
(=quantitatively). The formed salt must have a very low
solubility product
 Precipitate must be a pure compound (avoid co-
precipitation)
 Precipitate must be easy to filter
Why gravimetry is still in use, although
time-consuming and challenging:

 Accurate and precise (if done properly)

 Absolute method: No calibration
required
 Apparatus required is relatively
inexpensive
 Exercise:

 Lead (as Pb2+) can be determined by precipitation with

sodium iodide
 Write down the stoichiometric reaction formula
 What mass of NaI is needed to convert 1.00 g of
Pb(NO3)2 to PbI2?
 What mass of PbI2 will be formed?
 Exercise:
A sample of metallic tin (2.00 g) was reacted with iodine (8.80 g) in
a refluxing organic solvent, and an orange-yellow solid (A) (8.62 g)
was isolated. A qualitative elemental analysis of A showed it
contained only tin and iodide. A sample of A (2.0000 g ) was
accurately weighed into a pre-weighed silica crucible and roasted in
air (A reacts with H2O) to produce SnO2 (0.4810 g). A second
sample of A (2.0000 g) was dissolved in a small excess of nitric
acid, and excess silver nitrate added dropwise to precipitate silver
iodide, which was collected in a weighed sinter crucible, dried in an
oven at 110°C, and then cooled and weighed (mass of AgI
obtained=2.9986 g). When a sample of A was exposed to air for
several months, it became hydrated as shown by a second analysis
of the impure product, B, which showed Sn=17.92%, I=76.64%,
and H=0.61%.

(Sn=118.69, I=126.90, O=16.00, Ag=107.87, H=1.008)

 Exercise (continued):
1. From the amount of SnO2 obtained in the original analysis, calculate the
percentage of tin in A
2. From the amount of AgI obtained, calculate the percentage of iodide in A.
3. Assuming a molecular formula for A of SnaIb, the molecular weight of A is
therefore =118.69 x a + 126.90 x b.
100  a  118.69
Percentage tin X  (1)
M

100  b  126.90
Percentage iodide Y 
M
(2)

Use equations (1) and (2) and your calculated values for X and Y to
estimate the ratio b/a and determine the empirical formula of A.
4. A mass spectrum of A showed a cluster of peaks centred at a charge/mass
ratio m/z=626, and no other peaks at higher m/z. Assuming the observed
m/z corresponds to the approximate molar mass, M, what is the molecular
formula of A?
5. What is the percentage purity of the exposed sample, B, compared with A
(regard A as pure), and how many water molecules are there in B?
 Volumetric analysis
 Amount of analyte determined by measurement of
volume of a reagent needed to react with analyte
 Titrimetry: Determining the quantity of a reagent of
known concentration that is required to react
completely with the analyte
 Titration: Adding standard solution (titrant) to
solution of the analyte until reaction is complete.
Solution dispensed from burette to determine
volume of reagent required for reaction
 Requires that

 Reaction has a large equilibrium constant

 Reaction proceeds rapidly

 Titrimetric methods
 Acid-base titrations
 Precipitation titrations
 Volhard (Ag+ directly or Cl- via back titration)
 Complexometric titrations
 Cations with EDTA
 Redox titrations
 Manganometry, iodometry
 Spectrophotometric titrations
 Measures changes in UV-Vis spectra
 Potentiometric titrations
 Measures changes in potential (e.g. with pH
electrodes or Ion-selective electrodes)
 General terminology
• Equivalence point: Point in a titration when quantity of added
titrant is the exact amount necessary for stoichiometric reaction with
analyte.
This is the “ideal” point sought in a titration. In reality, we find the

• End point: Point reached when a (ideally sudden) physical change

in the solution occurs, which indicates the absence of unreacted
analyte. End points are often detected through an indicator

• Ideally, there is very little difference between the volumes for the
equivalence and end points. This difference is the titration error
• Can be determined with a blank titration

• Back titration: Excess of a standard solution added to consume

analyte is determined by addition of second standard. Required
when direct reaction is slow or unstable
 Typical titration curve
0
Decrease in concentration of analyte
-2 Note: semi-log plot

-4

-6

-8
log c

-10

-12

-14

-16
Equivalence point
-18
0 5 10 15 20 25 30 35 40 45 50

Volume/ amount of titrant added

 General terminology:
Standardisation
 Titrations require standard solutions:
Reagent of known concentration used to carry
out titration
 Primary standard: Solution of a highly purified
compound (>99.9%) that can be accurately weighed
 Serves as a reference material in a given volumetric titration
method. The accuracy of such methods is critically
dependent on the properties of this compound
 Must be stable (not decomposed during storage)
 Must be a compound that can be dried to remove residue
water
 Standard reference materials commercially available (SRMs)

 Secondary standard: Solution of titrant that has

been standardised by titrating a known amount of
primary standard (also commercially available)
 Precipitation Titrations
 Based on reactions that give products of low
solubility
 One of the oldest analytical techniques (mid 1800s)
 E.g. Volhard method for silver(I) titrations
 For direct analysis of silver ions or indirect detn. of
halides
 Titrant: NaSCN
Reaction 1: Ag+ + SCN¯ ⇌ AgSCN(s)
Ksp=[Ag+][SCN¯]=1.1 ×10-12
 Fe(III) acts as the indicator
Reaction 2: Fe3+ + SCN¯ ⇌ [Fe(SCN)]2+ (red)
Kf= [Fe(SCN)]2+ =1.4 ×102
[Fe3+][SCN¯]
 Red colour observed at [Fe(SCN)2+] = 6.4×10-6 M
 Volhard method for Ag+
 Exercise:
 Titrate 50 mL of 0.05 M Ag+ with 0.1 M KSCN
 What concentration of Fe3+ should be used to reduce titration error
to zero?
 Note: For zero titration error, the Fe(SCN)2+ colour should appear
when [Ag+] = [SCN-]
 Effect of solubility product
0

-2

-4

-6

-8
Log [Ag+]

-10
Ksp≈10-12
-12

-14

-16 Ksp≈10-18

-18
0 5 10 15 20 25 30 35 40 45 50

 The higher the solubility, the more difficult becomes the end point recognition
 Compleximetric titration
 Metal ion determination
 Metal ion reacts with ligand to form complex
 Can form soluble complexes or precipitates
 Equivalence point determined by indicator

pK1 = 0.0
 EDTA: Ethylenediamine tetraacetic acid; pK2 = 1.5
is a hexadentate ligand pK3 = 2.0
pK4 = 2.66
pK5 = 6.16
pK6 = 10.24
(n-4)+

[M(H2O)6]n+ + [H2(EDTA)]2- + 6 H 2O + 2 H +

ISO 6059: Determination of Hardness in water

Stoichiometric formation constants
for EDTA complexes
[MY(n-4)+] =KMY (Kf)
Mn++Y4- ⇌ MY(n-4)+
[Mn+][Y4-]

Cation KMY log KMY Cation KMY log KMY

Ag+ 2.1×107 7.32 Cu2+ 6.3×1018 18.80
Mg2+ 4.9×108 8.69 Zn2+ 3.2×1016 16.50
Ca2+ 5.0×1010 10.70 Cd2+ 2.9×1016 16.46
Sr2+ 4.3×108 8.63 Hg2+ 6.3×1021 21.80
Ba2+ 5.8×107 7.76 Pb2+ 1.1×1018 18.04
Mn2+ 6.2×1013 13.79 Al3+ 1.3×1016 16.13
Fe2+ 2.1×1014 14.33 Fe3+ 1.3×1025 25.10
Co2+ 2.0×1016 16.31 V3+ 7.9×1025 25.90
Ni2+ 4.2×1018 18.62 Th4+ 1.6×1023 23.20
 Titration curve shape depends on
formation constant
[MY(n-4)+]
Mn++Y4- ⇌ MY(n-4)+ [Mn+][Y4-]
=KMY (or Kf)

Titration curves for 50 mL of 0.01 mol/L cation solutions at pH 6.0.

 Ca2+ has smallest formation constant (weakest EDTA complex)

 Fe3+ has largest formation constant (strongest EDTA complex)
 Effect of pH
 Depending on pH, only a certain portion of EDTA is
present as Y4-: [Y4-] = aY4- [EDTA]total
 The value of aY4- decreases with pH
1,2-Diaminoethane-N,N,N',N'-tetraethanoic acid, Sequestric acid pH aY4- at 20°C
100
0 ligand
Free 1.3×10-23
Y4- AH
1 1.9×10-18
HY3-
90
AH2
80 H2 Y2- 2
AH3 3.3×10-14
AH4
70 3 2.6×10-11
4 3.8×10-9
60
5 3.7×10-7
50
6 2.3×10-5
40 7 5.0×10-4
30 H 3Y - 8 5.6×10-3
20
9 5.4×10-2
10 0.36
10
11 0.85
0
2 4 6 8 10 12
12 0.98
pH 13 1.00
14 1.00
Speciation curve
 Effect of pH
 This leads to an apparent reduction in stability:
[Mn ][Y 4 ] [Mn ] a Y4 - [EDTA] total
K K
[MY(n -4) ] [MY(n -4) ]

 Significant for complexes with small K values:

Influence of pH on the titration of 0.01 mol/L

Ca2+ (50 mL) with 0.01 mol/L EDTA.
Minimum pH needed for the satisfactory titration of
various cations with EDTA
 Endpoint recognition in
Titrations with EDTA
 Indicator for EDTA titrations: Eriochrome Black T
 Different forms of indicator ( -, 2-, 3- ) have
different colours
M n-3

+ Mn+ + 2H+
(red)

H2O + H2In- ⇌ HIn2- + H3O+ Ka1 = 5×10-7; pKa = 6.3

(red) (blue)
H2O + HIn2- ⇌ In3- + H3O+ Ka2 = 2.8×10-12; pKa = 11.6
(orange)

Kf for M(In) < Kf for M(EDTA): Solution stays red

until no more M is left for complexation with ET
pH must be > 6.3 to see colour change to blue
 Summary
 Both gravimetric and volumetric methods
require an understanding of the underlying
Chemistry
 Gravimetry: absolute method, no
standardisation required (but accuracy of a
given method must be tested)

 Titrimetry: careful standardisation is

required to achieve satisfactory accuracy
 Exercise

 Find and list gravimetric and/or volumetric

methods that may be commonly used in a
commercial Analytical Lab