CHM 256

CHAPTER 1 : INTRODUCTION : ANALYTICAL CHEMISTRY

CONCENTRATION

Molar Concentration (Molarity)

1 M (molar) = number of moles of solute in one liter of ……………… ?

Molarity = mol of solute / L of solution

or mmol of solute / mL of solution (mmol = millimole)

Equivalent

Depends on the purpose of the reagent (how is it going to be used)

Ex: In acid-base titration,

1 eq (equivalent) of acid = the amount of acid that gives 1 mol of H +
1 eq of base = the amount of base that gives 1 mol of OH-

Thus,
1 mol of HCl = 1 eq; 1 mol of H2SO4 = 2 eq
1 mol of NaOH = 1 eq; 1 mol of Ba(OH)2 = 2 eq

1 meq = 1/1000 eq

Normality (N)

N = no of eq / vol of solution (L) or meq/mL

1 M HCl = ……… N ?

1 M Ba(OH)2 = ………… N ?

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Percent Concentration

Weight percent (w/w%) = ?

Volume percent (v/v%) = ?

Weight/volume percent (w/v%) = ?

Weight percent - normally used for commercial aqueous reagents.

Volume percent - commonly used for liquid in liquid solutions.

Ex: 5% (v/v) ethanol in water
(5 mL ethanol added with water to 100 mL)

Weight/volume percent - usually used for dilute solutions of solid reagents in

water.

Parts per thousand / million / billion

Abbreviation: ppt, ppm, ppb

Concentration in ppt = mass of solute x 103

mass of solution

or mass of solute (g)

volume of solution (L)

Concentration in ppm = mass of solute x …………… ?

mass of solution

or ?

Concentration in ppb = mass of solute x …………… ?

mass of solution

or ?

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Problem:
Calculate the concentration of S (in ppm) in 0.05 M Na2S2O3.
(Na = 23.0 , S = 32.1 , O = 16.0)

Specific Gravity (density)

Abbreviation: sp. gr.

Problem:
Calculate the molar concentration of a concentrated sulfuric acid which has
the following specifications:
sp. gr. = 1.84 g/mL

conc (% w/w) = 96%

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Exercise

1. A 250 mL Ba(OH)2 solution which is used for acid-base titration contains 4.50 g of
Ba(OH)2. Calculate the concentration of Ba(OH)2 as:
a. Molarity b. w/v percent c. ppt
d. ppm e. ppb

2. Ethanol has a density of 0.79 g/mL. If 36.2 mL of ethanol is mixed with water to a
volume of 200 mL, calculate the concentration of the ethanol solution in:
a. v/v percent b. w/v percent c. molarity

3. A commercial sulfuric acid contains 97.5% H2SO4 (w/w) and has a specific gravity of
1.84 g/mL. Calculate the molarity of this solution.

4. Calculate the concentration of the following in ppm.

a. Cu in 0.15 g/L Cu(NO3)2
b. Al in 84 mg/L Al2(SO4)3
c. Na in a 500 mL solution containing 0.120 g NaCl and 0.240 g Na2CO3
d. K in 0.020 M K2SO4.

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CHAPTER 2 : EVALUATION OF EXPERIMENTAL DATA

Reporting Analytical Data

The Significant Figure Convention

Significant figure – all the certain digits and the first uncertain digit.
Ex:
Buret reading can be estimated to the nearest  0.02 mL.
The result can be reported as, eg. 30.24 mL.
- the first 3 digits are certain.
- the last digit is uncertain.

31.24 mL => 4 significant figures

0.03124 L => .......... significant figures ?

31.2 mL => ........................ ?

542.0 => ........................ ?

542.00 => ........................ ?

0.00300 => ........................ ?

2000.0 mL => ........................ ?

2000 mL => confusing 2006 mL => ........................ ?

- use scientific notation,

2.0 x 103 mL 2 significant figures

2.000 x 103 => .................................... ?

9.467 x 108 => ..................................... ?

9.467 x 10-15 => ..................................... ?

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Significant Figures in Calculations

Addition/Subtraction

Ex:

i) 3.4 + 0.020 + 7.31

3.4
0.020
7.3 1
10.730 Ans = ....................... ?

ii) 2.62 + 0.83 - 1.523

Multiplication/Division

Number of significant figure in the answer = the smallest number of significant

figure in the original number.

Ex:
i) 34.7 x 0.59 x 4.824 = 98.761752 (from calculator)
?

ii) 2.35 / 15.6832

?

iii) (426 + 0.86) x 0.068214

?

Rounding Data

Rounding number 5 => to the nearest even number

Ex: 52.35  52.4 52.45  52.4

Rounding results for complex calculations

- postpone rounding until the calculation is completed.

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Accuracy and Precision

Example:
A water sample contains 1000 ppm of calcium. When four different methods
were used to determine the Ca concentration in the water, the following results
were obtained: (all results given in ppm)

Method 1 : 978 988 992 1005 1008

Mean = (978 + 988 + 992 + 1005 + 1008) / 5 = 994.2 ~ 994 ppm

Method 2 : 994 995 996 996 998

Mean = ……………… ?

Method 3 : 950 952 953 954 955

Mean = ……………… ?

Method 4 : 947 952 959 969 975

Mean = ……………… ?

True value = ………………… ?

Accuracy
- Closeness of the measurement to its true value.

Precision
- Closeness of the results that have been obtained in exactly the same way.
- Reproducibility.

Method 1 : Low precision, High accuracy

Method 2 : ?

Method 3 : ?

Method 4 : ?

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Errors in Chemical Analysis

Calculation of Error

Absolute error

Eabs = xi - xt where : xi = value from measurement

xt = true or accepted value

Relative error

Er = xi - xt x 100%
xt

For method 1 :

Absolute error, Eabs = ?

Relative error, Er =

Types of Error

Random (Indeterminate) Error

- the scattering of data around a mean value.
- reflected by its precision.
Higher precision - lower random error

Systematic (Determinate) Error

- difference between the mean value and the true value
- causes the results to be all high or all low
- leads to bias in measurement technique.
- reflects the accuracy.
High accuracy – low systematic error.

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Causes of Systematic Error

i) Instrument error – caused by imperfection or instability of measuring devices.

Ex:
- pipets, burets, volumetric flasks may have volume different from indicated.
- may be due to wear and tear.
- used at temperature that differs significantly from calibration
temperature.
- Electronic devices that have dirty electronic circuits

ii) Method error – caused by nonideal chemical or physical behaviour of the

reagents.
Including:
Low purity of reagents.
Slowness of reaction.
Incomplete reaction (reversible).
Instability of reagent.
Side reactions that interfere with the measurement process.

Ex: In volumetric analysis (titration)

- small excess of reagent required to cause the colour change of an indicator.

iii) Personal error – due to personal judgements in taking experimental data.

1. Perception/disability
Ex: - the colour of solution at the end point of titration.
- the level of liquid with respect to a graduation in buret or pipet.
- the reaction time in pressing the stop watch button.

Personal disability may cause personal error. (ex: colour blind)

2. Prejudice
- tendency to estimate/adjust reading in the direction that increases
precision in a set of results.
- when there is a presumed true value of the measurement - tendency to
cause the result to be close to this value.
- Number bias
- preference of round number over unrounded.
- favouring the even number over odd number.

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Effects of Systematic Errors on Analytical Results

Constant Error
The magnitude of the error does not depend on the size of the quantity measured.
Ex: The excess reagent required to cause a colour change in a titration.
- does not depend on the volume of the reagent.
- more serious when the magnitude of the measurement is small.
- (absolute error is constant)

Proportional Error
The magnitude of the error is proportional to the value of the quantity being
measured.
Ex: Interference by contamination in reagents.
- (relative error is constant)

STATISTICAL EVALUATION OF DATA

Samples and Populations

Sample - a finite number of experimental observations (data).

Population - an infinite number of data

- theoretical

Population mean,  ?

Sample mean, ?

If there is no systematic error, then population mean is the true value of the
measured quantity.

The value of x normally differs from . As the number of measurement increases, x

approaches the value of .

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The population standard deviation, .

?

The sample standard deviation, s.

?

The standard deviation reflects the random error of the measurement.

Mode and Median

Mode – the most frequent value in a data set.

Ex: 65, 63, 66, 61, 63, 67, 64

Mode = .............. ?

Median – the middle value in a data set.

Ex: In the above set.

Arrange in increasing order:

61 63 63 64 65 66 67

There are 7 entries. Then, median is the 4th entry = ................ ?

Ex: 13.4 13.6 13.7 13.8 13.9 13.9

6 entries. Thus, median = .................................

= ................................. ?

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The Gaussian Curve

Ordinarily the distribution of analytical data follows the normal distribution curve
(Gaussian curve)
Frequency

Measured value
Mean

Which curve has a higher standard deviation? ....................... ?

Which curve has a higher random error? .......................... ?

Accuracy and the Normal Curve

True value Mean

Systematic error = ....................................................................... ?

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Confidence Limits

Confidence Limits - range of values around a mean with a certain degree of

certainty.

Confidence level - degree of certainty.

TABLE 1 Values of t for Various Level of Probability

Degrees of Factor for Confidence Interval

Freedom 80% 90% 95% 99% 99.9%

1 3.08 6.31 12.7 63.7 637

2 1.89 2.92 4.30 9.92 31.6
3 1.64 2.35 3.18 5.84 12.9
4 1.53 2.13 2.78 4.60 8.61
5 1.48 2.02 2.57 4.03 6.87
6 1.44 1.94 2.45 3.71 5.96
7 1.42 1.90 2.36 3.50 5.41
8 1.40 1.86 2.31 3.36 5.04
9 1.38 1.83 2.26 3.25 4.78
10 1.37 1.81 2.23 3.17 4.59
∞ 1.28 1.64 1.96 2.58 3.29

Confidence limits for  = ?

Problem:
The following results were obtained from a determination of Hg content in a
water sample using atomic absorption spectrophotometry.

Hg content (ppm) 1.80 1.58 1.64

Calculate the 80% and 90% confidence limits for the mean value.

Ans:

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Detecting Gross Errors

Outlier – a data point that differs excessively from the mean value in a data set.

Q test

Qexp = ?

xq = the questionable result (the outlier)

xn = its nearest neighbour
xhigh = the highest value
xlow = the lowest value

If Qexp > Qcrit, then ?

TABLE 2 Critical Values for the Rejection Quotient Q

Qcrit
Number of
Observations 90% Confidence 95% Confidence 99% Confidence

3 0.941 0.970 0.994

4 0.765 0.829 0.926
5 0.642 0.710 0.821
6 0.560 0.625 0.740
7 0.507 0.568 0.680
8 0.468 0.526 0.634
9 0.437 0.493 0.598
10 0.412 0.466 0.568

Ex: 56.04 55.95 56.00 56.23 56.08

i) Identify the outlier

ii) Using Q test justify whether it should be accepted or rejected at a 90%

confidence level.
?

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Exercise

1. The following table shows 2 sets of data obtained from the determination of Fe in a
standard solution using two different methods. The real concentration of Fe in the
standard solution is 200 ppm.

Method Concentration (ppm)

1 185 183 184 182 183 186

2 201 212 205 208 198 210

a. Calculate the mean for each set of data.

b. Which method is more precise?
c. Which method is more accurate?
d. Which method has a higher random error?
e. Calculate the systematic error for Method 1 and Method 2 as absolute error and
relative error.

2. State whether the following errors are caused by instrument, method or personal
(operative) factor.
a. Using a reagent which is not pure.
b. Using an analytical balance which was not calibrated.
c. When NaOH is titrated into an acid using phenolphthalein indicator, the end point
is justified when the colour of the solution turns to strong pink.

3. For each error in question 6 above, state whether it is constant or proportional.

4. What is the number of significant figures in the following?

a. 1.324 b. 1.206 c. 0.0045 d. 0.065900
8
e. 6.27 x 10 f. 300.0

5. Give the answers to the following calculations in the correct significant figure.
a. 6.52 + 0.004 + 27.9
b. 2.18 + 0.003
c. 5.62 - 0.343
d. 4.32 x 148.7 x 0.08314
e. 5.4 x 6.023 x 1023
f. 14.33 / 2.00
g. (4.37 + 0.28) x 15.625

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6. Two methods, A and B were used to determine the concentration of a standard

copper solution which contains 100 ppm Cu. The following figure shows the
distribution curves of the data sets obtained from both methods.

A
B

83 100 109 Cu concentration, ppm

a. Which method is more accurate?

b. Which method is more precise?
c. Which method has a higher random error?
d. Which method has a higher systematic error?
e. Calculate the relative standard error for both methods.

7. The following table shows a set of data obtained from the determination of Fe in a
water sample.

Measurement 1 2 3 4 5 6
Fe 201 212 205 208 198 210
concentration
(ppm)

a. Calculate the mean, median, standard deviation and relative standard deviation
of the data set.
b. Determine the 90% confidence limit of the Fe concentration in the sample.

8. The following data was obtained from a determination of palmitic acid content in a
palm oil sample by a gas chromatographic method. Five measurements were made.
The set of data obtained was as follows.

Measurement 1 2 3 4 5

Palmitic acid 33.9 32.3 34.1 33.7 34.4

Content (g/100 g oil)

a. Identify the outlier in the data set.

b. Using a Q-test justify whether the outlier should be rejected or accepted at a
90% confidence level.
c. Calculate the mean and standard deviation of the data set after the Q-test has
been done.

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CHAPTER 3: APPARATUS, TECHNIQUES AND REAGENTS

Analytical Balance
- an instrument to measure mass.
- precision of at least 1 part in 105 at maximum capacity.

Sources of error.

i. Correction for buoyancy.

- if the density of the object being weighed differs significantly from that of
standard mass. For most solids error is less than 0.1%.

ii. Temperature effect

- when temperature of object being weighed is higher than surrounding.

- air in the container has a lower density than surrounding air.
- convection air currents exert a buoyant effect.

Desiccators
To keep dried materials – to minimize uptake of moisture.

Desiccant

Desiccants – Ex: anhydrous calcium sulphate, silica gel, activated alumina.

- can be impregnated with cobalt salt – as indicator.
- colour changes from blue to pink when desiccant is exhausted.
- regenerated by heating in oven.

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Heating Apparatus

Bunsen Burner
- cannot control temperature.

Hotplates
- electrically heated.
- have a temperature control knob.
- some are incorporated with magnetic stirrer.

Electric Ovens
- temperature range from room temperature to about 250 – 300 oC.
- mainly used for drying precipitates or solids.

Furnaces
- for heating at higher temperatures.
- maximum temperature is above 1200 oC.

Water Baths
- equipped with a thermostat to control temperature.
- for carrying out reactions at desired temperature.

Filtration Apparatus and Techniques

The simplest apparatus

- a filter funnel fitted with filter paper.

Filter crucible – incorporated with sintered-glass.

Sintered-glass

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Buchner Funnel

- usually used in vacuum filtration.

- filter paper is placed on the plate.

suction

Reagents

Use reagents of the highest purity available.

- analytical grade reagents.

Care should be taken in handling chemical reagents.

- do not return any reagent to the reagent bottle.
- never insert a pipette into the reagent bottle.
- never let the bottle’s mouth or the inside of the cap to get in contact with
anything that could contaminate the reagent.

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CLEANING AND CALIBRATING GLASSWARE

Always label beakers, flasks, etc.

Cleaning – with hot detergent

Properly cleaned glassware – coated with a uniform, unbroken film of water.

It is seldom necessary to dry the interior surface of glassware before use.

Apparatus for the Precise Measurement of Volume.

Pipette, burette and volumetric flask.

Pipette and burette – to deliver (marked as TD)

Volumetric flask – to contain (marked as TC)

Calibrating a pipette.

- weigh a clean and dry receiver to the nearest milligram.

- transfer water from the pipette into the receiver.
- weigh the receiver with its content.
- calculate the mass of the water.
- calculate the volume of the water.
volume = weight x volume per 1.000 g of water
(volume of water varies with temperature)

Calibrating a burette

- same procedure as calibrating a pipette, except that a burette can be calibrated

at different segments.

Calibrating a volumetric flask

- weigh a clean and dry volumetric flask.

- fill the flask with water to the mark.
- weigh the flask with its content.
- calculate the weight of the water.
- calculate the volume of the water at the temperature.

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CHAPTER 4: BASIC REQUIREMENTS FOR ANALYSIS

Sampling
- a process of obtaining a representative fraction from the bulk material.
Samples must be representative (must represent the bulk material)

Pretreatment of solid samples

- the substance of interest is extracted from the sample.
Ex: an organic compound in a sample can be extracted using an organic solvent.

Dissolution of Samples
- for certain analysis the sample need to be dissolved completely.
Organic substances – dissolve in organic solvent.
Inorganic substance – dissolve in water, acids or alkalis.

Insoluble materials – treated with suitable chemicals.

Ex:
If the sample is a metal – use concentrated HCl or HNO3 to dissolve it.
More unreactive metal – use aqua regia.
Aqua regia is a mixture of 75% HCl and 25% HNO3.
It can react with unreactive metals, such as gold and platinum.

Wet ashing
- an organic sample is decomposed by a strong oxidizing agent such as a
concentrated acid (H2SO4, HNO3 or HClO4 ) or a mixture of these.
- inorganic matter, such as metals will remain in the sample.

Dry ashing
- the process of oxidizing an organic sample with oxygen or air at a high
temperature leaving the inorganic component for analysis.

The simplest method of dry ashing – heat the sample over a flame in an open
crucible until all organic matter has been oxidized.

Dry ashing also can be carried out in a muffle furnace.

Dry ashing of a precipitate can be carried out with the filter paper intact.
- use ashless filter paper.

Ashless filter paper – a filter paper that leaves a negligible amount of residue
after being ignited.
- manufactured by treating the paper with HCl and HF to remove metallic impurities
and silica.

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STANDARD SOLUTIONS

Primary Standard

- a reference material used in volumetric (titrimetric) analysis.

Important requirements for a primary standard

1. High purity.
2. Atmospheric stability.
3. Absence of hydrated water – composition of solid does not change with
variations in relative humidity.
4. Reasonable solubility in the titration medium.
5. Reasonably large molecular weight.

Standard Solutions
- used as titrants

Desirable properties of standard solutions

1. Be sufficiently stable.
- no frequent standardization is required.

2. React rapidly with the analyte.

3. React completely with the analyte.

- for satisfactory end point.

4. Undergo a selective reaction with the analyte.

Example:
NaOH cannot be used as a primary standard. It is standardized against potassium
hydrogen phthalate, KHP. (KHC8H4O4)

NaOH is a secondary standard.

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CHAPTER 5: VOLUMETRIC ANALYSIS

Titration

A titration is performed by adding a standard solution (standard titrant) into a

solution of the analyte.

Equivalence point – a point where the amount of titrant is chemically equivalent to

the amount of analyte.

End point – a point where the physical change associated with the chemical
equivalence is observed.

Ex: When using an indicator – the end point is a point where the colour change of
the indicator is observed.

Volumetric Calculation

Suppose that the reaction in a titration is a follows:

a A + b B  products

Thus: mol A / mol B = a/b

or mmol A / mmol B = a/b

(mmol = ?

=> MAVA / MBVB = ……… (M = molarity, V = volume) ?

or ?

Ex:
H2SO4 + 2 KOH  K2SO4 + 2 H2O
?

( A = H2SO4 , B = KOH )

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Acid-Base Titration (Neutralization)

Standard Solutions

Standard solutions are strong acids or strong bases because they react completely
with the analyte, therefore giving sharper end points.

Nitric acid is seldom used because its oxidizing properties can cause side reactions.

Acid standard solutions are standardized by titrating with anhydrous sodium

carbonate (a primary standard).

Chemical equation :

Standard solution of a base – normally from solid sodium hydroxide or potassium

hydroxide.

- standardized against potassium hydrogen phthalate.

Chemical equation:
?

Autoionization of Water

Water dissociates into hydrogen ion, H + and hydroxide ion, OH -

H2O(l) ?

At 25 oC, [H +] = [OH -] = ……………… ?

The equilibrium constant, Kc = [H +][OH -]

or Kw = [H +][OH -] = ?

When an acid is added, [H+] > 10-7 => [OH-] < 10-7
When a base is added, [OH-] > 10-7 => [H+] < 10-7

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Ex:
Calculate the concentrations of hydrogen and hydroxide ions in 0.01 M HCl.

The pH Scale

The pH scale provides a convenient way to represent solution acidity.

pH is defined as :
pH = .......... ?

Thus, when [H+] = 1.0 x 10-7 M, pH =

= ?

In an acidic solution, [H+] > 10-7 => pH < 7

Ex: [H+] = 1.0 x 10-5 M, Then pH = ?
=

In a basic solution, [H+] < 10-7 => pH > 7

Ex: [H+] = 1.0 x 10-8 M, Then pH = 8.0

The pOH Scale

pOH = -log10[OH-]
When pH < 7, then pOH > 7

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Relationship between pH and pOH

Ex:
Calculate the pH and pOH of 0.1 M HCl.

Ex:
The pH of a sample of human blood was 7.41. Calculate pOH, [H+] and [OH-] for the
sample.

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The pH Change in a Titration

Strong acid titrated with strong base.

(Titration of strong acid with strong base)

Ex: 20.0 mL 0.10 M HNO3 titrated with 0.10 M NaOH.

No of mol of HNO3 = 0.10 M x 20 mL / 1000

= 0.0020 mol or 2.0 mmol (1 mol = 1000 mmol)

or 0.10 M x 20 mL
= 2.0 mmol

a) Before titration (no NaOH added)

b) 10 mL NaOH added

c) 19 mL NaOH added

d) 19.9 mL NaOH added

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e) 20.0 mL NaOH added

f) 20.1 mL NaOH added

g) 21 mL NaOH added

Titration Curve

Titration of strong acid with strong base (base into acid)

Strong acid + strong base  neutral salt

pH

7.0

Volume of titrant (base)

Equivalence point

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Titration of weak acid with strong base

Weak acid + strong base  basic salt

pH

7.0

Volume of titrant (base)

Equivalence point

Acid-base Indicator

A weak organic acid or weak organic base whose colour is different in the acid form
and the base form.

Acid-type indicator

Base-type indicator

pH Range of Indicators

pH range of an indicator is a pH range where there is a visible colour change of the

indicator.

Ex:
?

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Choosing an Indicator

A suitable indicator is an indicator which gives a sharp colour change at the

equivalence point.

Ex: Indicator pH Range Acid – base Colour

Methyl Orange 2.9 – 4.5 Red – yellow

Phenolphthalein 7.8 - 10.0 Colourless – Pink

Titration of strong acid with strong base

pH

Phenolphthalein

7.0

Methyl orange

Volume of titrant (base)

Equivalence point

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Back Titration

Back titration is done when an excess amount of standard solution is

required for a complete reaction with the analyte. Thus, the analyte cannot be
titrated directly. Instead, an excess amount of standard solution is added to the
analyte. The amount of excess reagent is determined by titration (back titration).

Example:
The determination of CaCO3 content in a limestone sample. The limestone
sample is reacted with standard HCl. However, excess HCl is required for a
complete reaction. The amount of excess HCl is determined by titration with a
standard NaOH.

Problem:
50.0 mL of 1.025 M HCl is added to 1.520 g of limestone which contains
mainly of CaCO3. The following reaction took place.

CaCO3 + 2 HCl  CaCl2 + H2O + CO2

The excess acid was back-titrated with 24.3 mL 0.967 M NaOH. Calculate the
percentage of calcium carbonate in the limestone.

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Determination of Nitrogen Content by Kjeldahl Method

- Used to determine total organic nitrogen in a sample.

- Widely used to determine the protein content in food.

The sample is decomposed in hot, concentrated sulphuric acid to convert organic

nitrogen to ammonium ion. Then a base, such as NaOH is added to the solution.
Ammonium is converted by the base to ammonia.

NH4+ + OH-  NH3 + H2O

The ammonia is distilled and collected in a known amount of excess acid. The excess
acid is back titrated with NaOH.

The protein content is calculated by multiplying the percentage of nitrogen by a

certain factor. The factor depends on the type of food.
Ex: 6.25 for meats, 6.38 for dairy products, 5.70 for cereals.

Problem:
A 0.7121 g sample of a wheat flour was analyzed by the Kjeldahl method. The
ammonia formed was distilled into 25.00 mL of 0.04977 M HCl. The excess HCl was
back-titrated with 3.97 mL of 0.04012 M NaOH. Calculate the percent of protein in
the flour. (There is 5.70 g protein for each gram N in the flour)

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Exercise

1. For each of the standard/unknown titration pair below, write the reaction equation
and calculate the concentration of the unknown.

Standard solution Unknown solution

Compound Volume Concentration Compound Volume Concentration

(mL) (M) (mL) (M)

a. NaOH 15.25 0.1025 HCl 20.0

b. H2SO4 22.4 0.0996 KOH 25.0

c. NaOH 25.6 0.1985 CH3COOH 10.0

2. A standard KOH solution was prepared by dissolving about 5.5 g of KOH in about 1
liter of water. This solution was then standardized by titration against 22.87 g/L
potassium hydrogen phthalate, KHC8H4O4 solution. 20.0 mL of the potassium
hydrogen phthalate requires 18.6 mL of the KOH solution. Calculate the
concentration of the KOH solution. (0.120 M)

3. 25.0 mL of 0.528 M sulfuric acid was added to 0.592 g sample of impure CuO and
the following reaction took place:
CuO + H2SO4  CuSO4 + H2O
The excess H2SO4 was titrated with 28.1 mL 0.489 M NaOH. Calculate the
percentage of CuO in the sample. (85 %)

4. 25 mL 0.2 M KOH is titrated with 0.2 M HCl. Calculate the pH when the volume of
HCl added is
a. 0 mL
b. 15 mL
c. 25 mL
d. 35 mL

5. A 0.958-g sample of canned fish was analyzed by the Kjeldahl method. The
ammonia liberated was collected in 25.0 mL of 0.2023 M HCl. The excess HCl was
titrated with 21.8 mL of 0.1047 M NaOH.
Calculate:
a. The percentage of nitrogen in the canned fish.
b. The percentage of protein in the canned fish.
(1 g of nitrogen is equivalent to 6.25 g of protein in the fish)
(4.06 %, 25.3 %)

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CHAPTER 6: GRAVIMETRIC ANALYSIS

Analysis based on the measurement of mass.

Two major types:

a) Precipitation
– The analyte is converted to a low solubility precipitate.
- The product (precipitate) is filtered, washed, then dried or converted to a
product of known composition.
- Then it is weighed.

Example:

b) Volatilization
- The analyte is volatilized or decomposed to a volatile product.
- measure the loss of mass in the sample.
- or collect the volatile product and weigh it.
- examples of volatile products: H2O, CO2.

Precipitation

The precipitate should have the following properties:

i) Free of contaminants
ii) Has low solubility so that no significant loss of solid occurs during filtration and
washing.
iii) Unreactive with the atmosphere.
iv) Of known composition after it is dried or ignited.

Ex:
?

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Particle Size

Particle size is inversely proportional to the relative supersaturation.

Relative supersaturation =
?

When relative supersaturation (RS) is high

- many small crystals.
- high surface area of crystals.
(high rate of crystallization)

When RS is low
- fewer, larger crystals.
- low surface area.

The advantages of using low RS.

i) Larger crystals – lower surface area
- less impurities adsorbed on the surface

ii) Slower rate of crystallization.

- lower chances for impurities to be trapped.

To keep RS low

1. Precipitate from a dilute solution – Q is low.

2. Add the precipitating agent slowly, while stirring – Q is low.
3. Precipitate from hot solution.
- At higher temperature the solubility is higher.
- S is high
The mixture is then cooled down slowly.

A slight excess of precipitating reagent should be added to assure complete

precipitation.

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Digestion of the Precipitate

- heating the precipitate in the precipitation medium.

- small crystals coagulate to form particles – smaller surface area – less impurities.
- the trapped particles are removed from the crystals.

Peptization

- reverse of coagulation
- coagulated particles are broken into small particles – washed away trough the
filter paper
- a result of washing the precipitate with water.
- to avoid peptization – use electrolyte solutions instead of water. The electrolyte
should be volatile at high temperature.
Ex: HNO3 or NH4NO3 for AgCl precipitate.

Drying and Ignition of Precipitates

- After filtration, the precipitate is heated to a constant mass. Heating removes

the solvent and volatile compounds present in the precipitate.
- Ignition – heating at a higher temperature to decompose the solid to a compound
of known composition.

The Choice of Precipitating Reagent

Choose a cation or anion that forms a low solubility salt with the ion to be
analyzed.

Ex: To determine halides: Cl-, Br-, I- , use soluble ................ ?

To determine SO42- , use soluble ................... ?

To determine Ag+ use ................ ?

To determine Ba2+ use ................. ?

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Volatilization

Ex: Determination of carbonates in rock by reaction with HCl.

CaCO3(s) + 2 HCl(aq)  CaCl2(aq) + H2O(l) + CO2(g)

CO2 can be collected using absorbent containing NaOH.

2 NaOH(s) + CO2(g)  Na2CO3(s) + H2O(l)

Mass of CO2 = increase in mass of absorbent.

Problems

1. A solution containing 0.523 g sample of impure MgCl2 is treated with excess

AgNO3 and 1.552 g of AgCl is obtained. Calculate the purity of MgCl2.

2. Calcium in a 250 mL solution is precipitated as CaC2O4. The solid is ignited to

2.13 g CaO. Calculate the concentration of Ca (in g/L) in the solution.

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Exercise

1. The sulphate ion in a 100 mL solution containing Na2SO4 was precipitated with
BaCl2 and 1.917 g of BaSO4 was obtained. Calculate the concentration of the
solution as gram Na2SO4 per liter solution.
(11.67 g/L)

2. 4.50 g of an organic compound was burned in excess oxygen and the CO2
produced was collected in an absorbent with a mass of 163.43 g. The final mass of
the absorbent was 171.45 g. Calculate the percentage of carbon in the organic
compound.
(48.7 %)

3. Pyrite ore (impure FeS2) is analyzed by converting the sulfur to sulfate and
precipitating BaSO4. If 4.152 g of BaSO4 was precipitated from 1.363 g of a pyrite
sample, determine the percentage of FeS2 in the sample.
(78.31 %)

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CHAPTER 7: CHROMATOGRAPHY

Chromatography – separation of components in a sample by distribution of the

components between 2 phases – stationary phase and mobile phase.

Stationary phase – at fixed position (does not move).

- can be solid or liquid.
Mobile phase – moves along the stationary phase.
- can be a liquid or gas.

Every component equilibrates/interacts between the stationary phase and the

mobile phase.
Xm Xs
The component either dissolves in the liquid/gas phase or adsorbs on the surface of
the solid particles of the stationary phase.

Separation is based on the different affinity of the components towards the

stationary phase or mobile phase.

Principle: Like dissolves like.

Polar compound (component) has a high affinity/solubility towards the ..................

..........................

Non-polar compound (component) has a high affinity/solubility towards the

................................................

The stationary phase and mobile phase will have different polarity. If the
stationary phase is polar, then the more polar compounds will be retained more
strongly than the less polar compounds. Thus, the component with lower polarity will
be eluted (carried by the mobile phase) faster. This causes the components to be
separated.

Partition Chromatography

Stationary phase – ...................................................................... ?

Mobile phase – liquid or gas.

If the mobile phase is a liquid then it is called liquid-liquid chromatography.

If the mobile phase is a gas then it is called gas-liquid chromatography (GLC).

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Adsorption Chromatography

Stationary phase – solid.

Mobile phase – liquid or gas.

Column Chromatography

The stationary phase is held on the surface of a solid support. The support is in the
form of small particles.

Examples of common supports:

?

The support is poured into a column. Then the mobile phase (eluent) is poured into
the column. This is followed by adding a small volume of the sample (analyte). Then
more mobile phase is added. The mobile phase elutes (moves) the analyte.

The choice of solvents

A suitable mobile/stationary phase combination should be chosen so that the

separation will take place effectively.

Example: If stationary phase – polar

mobile phase – non-polar.

A ................................... compound will be eluted faster than a .......................... compound.

Retention time - the time taken for a component (an analyte) to be eluted through
the column.

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Paper Chromatography
- a type of planar chromatography

Filter paper

Sample spots

Developing solvent

- A sample is spotted on a strip of filter paper.

- the chromatogram is developed by placing the bottom of the paper in a suitable
solvent.
- the solvent is drawn up the paper by capillary action.
- the components move up the paper at different rates, depending on their
solubility in the solvent and their degree of retention by the paper.

The spots of the solutes are detected by treatment with a reagent that forms
coloured derivative with the solute.

Eg: exposure to iodine vapour.

- Components are identified by Rf values.

Rf = ?

Distance traveled by solute = measured from ........................................... ?

The spots can be cut out of the paper and dissolved in other solvent for analysis.
Suitable for separation of small amounts of samples.

Paper is made of cellulose which is very hydrophilic.

- absorbs moisture from air – contains a thin layer of water on the surface of the
fiber.
The mechanism of separation in paper chromatography is liquid-liquid partition
chromatography.
- stationary phase = …………………………………………, mobile phase = …………………… ?

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Thin Layer Chromatography (TLC)

- a type of planar chromatography

Stationary phase - a thin layer of adsorbent coated on a plate (glass, aluminium or

plastic)
Most common adsorbent – silica gel or alumina.
These adsorbents contain hydroxyl groups on their surface – can adsorb polar
molecules.
- In most TLC – stationary phase is the solid adsorbent.

The technic of development in TLC is the same as for paper chromatography.

(Analytes are spotted on the plate and the bottom of the plate is then placed in the
developing solvent).

Components identified by Rf values.

Detection of the spots

- exposing the plate to iodine vapor.

- TLC plates pretreated with fluorescent dye – held under UV light – dark spot
appear at the sample spots.
- spraying the plate with sulfuric acid. After dried, the components appear as dark
spots.

For quantitative analysis – the spots are scraped out of the plate. Then dissolved in
suitable solvent.

Ion Exchange Chromatography

- used to separate anions or cations.

Stationary phase consists of polystyrene beads. (also called resins)

- contain free phenyl groups.

The phenyl groups can be treated with ionic functional groups.

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Cation Exchange Resins.

- acidic functional groups are added to phenyl group of the resin.

- two types of acidic functional groups,
i) Carboxylic acid, -COOH
ii) Sulfonic acid, -SO3H

These functional groups are added to the phenyl groups on the surface of the
resins.

The protons (H+) in these groups can exchange with other cations.

Example:
?

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Exchange capacity of a resin = total number of replaceable hydrogen per unit

weight of resin.
Number of H+ replaced = number of equivalence of cation.
Example: 1 mol H+ replaced by 1 mol Na+
2 mol H+ replaced by 1 mol Ca2+

Separation of cations is based on the their degree of retention by the resin.

Cations that are retained stronger by the resin will be eluted slower.
Anion Exchange Resin

The resin contains basic functional groups.

Example: Amine, -NH2.
In water this functional group exists as NH3+OH -.

Example of exchange reaction:

Applications of ion exchange chromatography

1. Purification of water (deionization of water)

Water is passed through a column of mixed ion exchange resin. The mixed resin
consists of cation exchange and anion exchange resins.

Example: When NaCl is passed through the column;

Na+ is replaced by .................. ?

Cl - is replaced by ................... ?

2. Analysis
- identification and quantification of ions.
- different ions are separated, then analyzed.

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