LECTURE NOTE SERIES

Analytical
CHEMISTRY
PART 1 - Basic Chemical Analysis

M. S. JHONG
 Content
Chapter Page
1. Introduction To Analytical Science 1
a. Classification of analysis
b. The scientific method
c. The sample
d. The analytical process
e. Measurement
f. Elementary statistics
g. Distribution of measurement
h. Student t-test
i. Rejection of data, Q-test
2. Solutions And Concentration 11
a. Concentration of Solution
i. Molarity
ii. Molality
iii. Normality
iv. Percentage Concentration
v. Dilute concentration units
b. Concentration Conversion
3. Volumetric Analysis 16
a. Basic principle of volumetric analysis
b. Primary standard
c. Secondary standard
d. Standardization
e. Acid-Base Titration
f. Back titration
g. Redox titration
h. Precipitation titration
i. Complexometric titration
4. Gravimetric Analysis 27
a. Properties of Precipitates and Precipitating Reagents
b. Particle Size and Filterability of Precipitates
c. Gravimetric Factor Method
5. Chromatography 31
a. Planar chromatography
i. Paper chromatography
ii. Thin layer chromatography
b. Column chromatography
 Chapter 1
Introduction to Analytical Science
ANALYTICAL SCIENCE DEFINED
The science that identification and/or quantification of any components of material is called
analytical science. The process of determination and identification of components in a
material is called analysis. When involves chemical processes, it is called chemical analysis or
analytical chemistry. The objects of analysis are termed analyte, and the environment of
analyte is found is called the matrix of the analyte.

CLASSIFICATIONS OF ANALYSIS
Classification can be based on whether the analysis is “qualitative” or “quantitative.”
Qualitative analysis is identification. Means an analysis carried out to determine only the
identity of analyte. Quantitative analysis, the other hand, is the analysis of a material for how
much of one or more components is present. Such an analysis is undertaken when the identity
of the components is already known and when it is important to also know the quantities of
these components.

THE SCIENTIFIC METHOD

At the core of sciences lies a problem-solving approach called the scientific method. The
scientific method has five basic steps, plus one feedback step:
1. Make an observation.
2. Ask a question.
3. Form a hypothesis, or testable explanation.
4. Make a prediction based on the hypothesis.
5. Test the prediction.
6. Iterate: use the results to make new hypotheses or predictions
Scientific method example: Failure to toast
1. Make an observation. - Let's suppose that you get two slices of bread, put them into
the toaster, and press the button. However, your bread does not toast. The
observation is “the toaster won’t toast’.
2. Ask a question. - Why didn't my bread get toasted?
3. Propose a hypothesis. - A hypothesis is a potential answer to the question, one that
can somehow be tested. For example, our hypothesis in this case could be that the
toast didn't toast because the electrical outlet is broken. This hypothesis is not
necessarily the right explanation. Instead, it's a possible explanation that we can test
to see if it is likely correct, or if we need to make a new hypothesis.

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 4. Make predictions. - A prediction is an outcome we'd expect to see if the hypothesis is
correct. In this case, we might predict that if the electrical outlet is broken, then
plugging the toaster into a different outlet should fix the problem.
5. Test the predictions. - To test the hypothesis, we need to make an observation or
perform an experiment associated with the prediction. For instance, in this case, we
would plug the toaster into a different outlet and see if it toasts.
a. If the toaster does toast, then the hypothesis is supported—likely correct.
b. If the toaster doesn't toast, then the hypothesis is not supported—likely
wrong.
6. Iterate. - The last step of the scientific method is to reflect on our results and use them
to guide our next steps.
a. If the hypothesis was supported, we might do additional tests to confirm it, or
revise it to be more specific. For instance, we might investigate why the outlet
is broken.
b. If the hypothesis was not supported, we would come up with a new
hypothesis. For instance, the next hypothesis might be that there's a broken
wire in the toaster.
In most cases, the scientific method is an iterative process. In other words, it's a cycle rather
than a straight line. The result of one go-round becomes feedback that improves the next
round of question asking.

THE SAMPLE
A term for the material under investigation is bulk system. Representative portion of the bulk
system is introduced into the laboratory for analysis. This portion is called a sample. The
rigorous laboratory operations that ultimately result in the identity or quantity of the analyte
in question. The representative sample it must truly represent the bulk system.

THE ANALYTICAL PROCESS

1. Obtain the sample. Sample must be representative; its integrity must be maintained;
chain of custody must be documented.
2. Prepare the sample. Drying the sample, crushing and homogenizing the sample,
dissolving the sample, extracting the analyse from the sample, etc. Exact steps needed
depend on the nature of the sample and the analysis method chosen.
3. Carry out the analysis method. A wide variety of “methods” are available (wet
methods and instrumental methods). Tasks include weight or volume measurements
on the sample, preparation of standard solutions, calibration of equipment, and the
collection of the required data.
4. Work the data. Involves calculations, graph plotting, and/or statistics.
5. Calculate and report results

MEASUREMENT
“Measurement” is the act of determining a target's size, length, weight, capacity, or other
aspect. There are a number of terms similar to “measure” but which vary according to the

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purpose (such as “weight,” “calculate,” and “quantify.”) In general, measurement can be
understood as one action within the term “instrumentation.”
Direct Measurement - measuring instruments such as Vernier calipers, micrometers, and
coordinate measuring machines are used to measure the dimensions of the target directly.
indirect Measurement - the dimensions are measured using measuring instruments such as
dial gauges that look at the difference between targets and reference devices such as gauge
blocks and ring gauges.

Units of Measurement
Scientific Units the SI and Metric Units, there are seven base units in the SI system:
1. the kilogram (kg), for mass
2. the second (s), for time
3. the kelvin (K), for temperature
4. the ampere (A), for electric current
5. he mole (mol), for the amount of a substance
6. the candela (cd), for luminous intensity
7. the meter (m), for distance

Volume and Density

volume: A unit of three-dimensional measure of space that comprises a length, a width, and
a height. It is measured in units of cubic centimetres in metric. The volume of a substance is
related to the quantity of the substance present at a defined temperature and pressure. The
volume of a substance can be measured in volumetric glassware, such as the volumetric flask
and the graduated cylinder.
density: A measure of the amount of matter contained in a given volume. Density indicates
how much of a substance occupies a specific volume at a defined temperature and pressure.
The density of a substance can be used to define the substance.

Concentration
In chemistry, the word "concentration" relates to the components of a mixture or solution.
Another definition is that concentration is the ratio of solute in a solution to either solvent or
total solution. Concentration is usually expressed in terms of mass per unit volume. However,
the solute concentration may also be expressed in moles or units of volume. Instead of
volume, concentration may be per unit mass. While usually applied to chemical solutions,
concentration may be calculated for any mixture.
Unit of Concentration:
1. Molarity (M) - moles of solute/liters of solution (not solvent!)
2. Mass Concentration (kg/m3 or g/L) - mass of solute/volume of solution
3. Normality (N) - grams active solute/liters of solution
4. Molality (m) - moles of solute/mass of solvent (not mass of solution!)

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 5. Mass Percent (%) - mass solute/mass solution x 100% (mass units are the same unit
for both solute and solution)
6. Volume Concentration (no unit) - volume of solute/volume of mixture (same units of
volume for each)
7. Number Concentration (1/m3) - number of entities (atoms, molecules, etc.) of a
component divided by the total volume of the mixture
8. Volume Percent (v/v%) - volume solute/volume solution x 100% (solute and solution
volumes are in the same units)
9. Mole Fraction (mol/mol) - moles of solute/total moles of species in the mixture
10. Mole Ratio (mol/mol) - moles of solute/total moles of all other species in the mixture
11. Mass Fraction (kg/kg or parts per) - mass of one fraction (could be multiple
solutes)/total mass of the mixture
12. Mass Ratio (kg/kg or parts per) - mass of solute/mass of all other constituents in the
mixture
13. PPM (parts per million) - a 100 ppm solution is 0.01%. The "parts per" notation, while
still in use, has largely been replaced by mole fraction
14. PPB (parts per billion) - typically used to express contamination of dilute solutions

ELEMENTARY STATISTICS
Errors
Errors in the analytical laboratory are basically of two types: determinate errors and
indeterminate errors. Determinate errors, also called systematic errors, are errors that were
known to have occurred. They may arise from avoidable sources, such as contamination,
wrongly calibrated instruments, reagent impurities, instrumental malfunctions, poor
sampling techniques, errors in calculations, etc. Results from laboratory work in which
avoidable determinate errors are known to have occurred must be rejected or, if the error
was a calculation error, recalculated.
Indeterminate errors, also called random errors, on the other hand, are errors that are not
specifically identified and are therefore impossible to avoid. A statistical analysis must be
performed to determine whether the results are far enough “off-track” so as to merit
rejection.

Definitions
1. Mean: It is calculated by adding together the numerical values of all measurements
and dividing this sum by the number of measurements.
2. Median: the “middle” value is sometimes important and is called the median. If the
total number of measurements is an even number, there is no single “middle” value.
In this case, the median is the average of two “middle” values.
3. Mode: The value that occurs most frequently in the series is called the “mode.”
4. Deviation: How much each measurement differs from the mean. Mathematically, the
deviation is calculated as follows:

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 𝑑 = (𝑚 − 𝑒)

in which d is the deviation, m is the mean, and e represents the individual

experimental measurement.
5. Sample Standard Deviation: The most common measure of the dispersion of data
around the mean for a limited number of samples (<20) is the sample standard
deviation:

(𝑑12 + 𝑑22 + 𝑑32 … . . )

𝑠=√
(𝑛 − 1)

in which n is the number of measurements. The term (n − 1) is referred to as the

number of
degrees of freedom, and s represents the standard deviation
6. Relative Standard Deviation: One final deviation parameter is the relative standard
deviation, RSD. It is obtained by dividing s by the mean

𝑠
𝑅𝑆𝐷 =
𝑚
Multiplying the RSD by 100 gives the percentage of RSD:
% 𝑟𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑒𝑟𝑟𝑜𝑟 = 𝑅𝑆𝐷 𝑥 100

Example 1 - The percent of moisture in a powdered pharmaceutical sample is determined by

six repetitions of the Karl Fisher method to be 3.048%, 3.035%, 3.053%, 3.044%, 3.049%, and
3.046%. What is the mean, median, mode, and sample standard deviation for these data?
Solution
The mean is the average of all measurements.
(3.048 + 3.035 + 3.053 + 3.044 + 3.049 + 3.046)
𝑚𝑒𝑎𝑛 = = 3.046
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The median is the “middle” value of an odd number of values. If there is an even number, the
median is the average of the two “middle” values.
(3.048 + 3.046)
𝑚𝑒𝑑𝑖𝑢𝑚 = = 3.047
2
The sample standard deviation is

0.0022 + 0.0112 + 0.0072 + 0.0022 + 0.0032 + 0.0002

𝑠=√ = 0.006
5

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Example 2- What is the percentage of RSD for the data in Example 1?
Solution
𝑠 0.006
%𝑅𝑆𝐷 = 𝑥100 = 𝑥100 = 0.20%
𝑚 3.046

DISTRIBUTION OF MEASUREMENTS
The normal distribution curves. For an entire population, the measurements are dispersed
around the mean with an equal “drop-off” from the mean in each direction. This mean is
recognized as the true mean because the entire population was analysed. The true mean is
designated as μ. The population standard deviation is associated with μ is designated as σ.
The more precise the data, the tighter the data points are bunched around the mean and the
smaller the σ. The less precise the data are, the less tight the data and the larger the σ.

STUDENT T-TEST
The true mean is the mean value at a certain degree of confidence for a real data set. The
confidence limit is the interval around the mean that probably contains the true mean, μ. The
confidence level is the probability (in percent) that the mean occurs in a given interval. For
example, a 95% confidence level means that the analyst is confident that for 95% of the tests
run, the sample will fall within the set limits. The student’s T method, is the method expresses
the true mean for an entire population (μ). The equation as follows:
𝑡𝑠
𝜇 =𝑚±
√𝑛
in which t is a constant depending on the confidence level and n is the number of
measurements. The values of t required for a desired confidence level and for a given number
of measurements are given in table below

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Example 3 - What is the true mean (with confidence interval) for the data in Example 1 using
Student’s t for the 95% confidence level?
Solution – Refer to n- 1 column, calculate the value on n-1, 6-1 = 5. At the first column. Then
refer to the 95% confidence column. Match the value of 5 in the same row at 95% and we get
the value of T which is 2.57. And applied to the equation above.
2.57𝑥0.006
𝜇 = 3.046 ±
√6
𝜇 = 3.046 ± 0.006

REJECTION OF DATA
Sometime a single measurement is so different from the others (the outlier). The decision
must be made as to whether this measurement should be “rejected,” meaning not included
in the calculation of the mean.
This measurement should not be immediately rejected as being “bad” because, in the
absence of a full investigation to determine a cause, it may, in fact, be legitimate. If a
legitimate measurement is rejected, then a bias is introduced, and the mean, while
assumed to be the correct answer, is actually flawed.
For small data sets (3 ≤ n ≤ 10), which are often encountered in chemical analysis, a simple
method to determine if an outlier is rejectable is the Q test. In this test, a value for Q is
calculated and compared with a table of Q values that represent a certain percentage of
confidence that the proposed rejection is valid. If the calculated Q value is greater than the
value from the table, then the suspect value is rejected and the mean recalculated. If the Q
value is less than or equal to the value from the table than the calculated mean is reported.
Q is defined as follows:

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 𝑔𝑎𝑝
𝑄=
𝑟𝑎𝑛𝑔𝑒
where the “gap” is the difference between the suspect value and it nearest neighbor and the
“range” is the difference between the lowest and highest values

Example 4 - Determine if any of the values in Example 1 should be rejected based on the Q
test at the 90% confidence level.
Solution - The six values realigned from lowest to highest are 3.035%, 3.044%, 3.046%,
3.048%, 3.049%, and 3.053%. The outlier would be 3.035%, since it has a larger gap (0.009)
from its nearest neighbour (3.044) than has 3.053. Thus,

𝑔𝑎𝑝 0.009
𝑄= = = 0.5
𝑟𝑎𝑛𝑔𝑒 0.018
Since the Q value for 6 measurements is 0.56 (table) and since the calculated value (0.5) is
less, the suspect value cannot be rejected.

ABSOLUTE AND RELATIVE ERROR

Absolute error is defined as the difference between the actual value and the measured value
of a quantity. The absolute error is calculated by the subtraction of the actual value and the
measured value of a quantity. If the actual value is x0 and the measured value is x, the absolute
error is expressed as,
△ 𝑋 = 𝑋0 − 𝑋

Example 5 - Suppose, we are measuring the length of an eraser. The actual length is 35 mm
and the measured length is 34.13 mm.
Solution - So, The Absolute Error = Actual Length - Measured Length
= (35-34.13) mm = 0.87 mm

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The relative error is calculated by the ratio of absolute error and the actual value of the
quantity. If the absolute error of the measurement is ∆x, the actual value is x 0, the measured
value is x, the relative error is expressed as,
(𝑋0 − 𝑋) △ 𝑋
𝑋𝑟 = =
𝑋0 𝑋0
Here, xr is the relative error.
Example 6 - Suppose, the actual length of an eraser is 35 mm. Now, the absolute error = (35-
34.13) mm = 0.87 mm.
Solution - So, the relative error = absolute error/actual length
= 0.87/35
= 0.02485

SIGNIFICANT FIGURES
Significant figures of a number are digits which contribute to the precision of that number.
Numbers that do not contribute any precision and should not be counted as a significant
number are:
1. leading or trailing zeros
2. digits that are introduced by calculations that give the number more precision than
the original data allows.

Rules For Determining If a Number Is Significant or Not

1. All non-zero digits are considered significant. For example, 91 has two significant
figures (9 and 1), while 123.45 has five significant figures (1, 2, 3, 4, and 5).
2. Zeros appearing between two non-zero digits (trapped zeros) are significant. Example:
101.12 has five significant figures: 1, 0, 1, 1, and 2.
3. Leading zeros (zeros before non-zero numbers) are not significant. For example,
0.00052 has two significant figures: 5 and 2.
4. Trailing zeros (zeros after non-zero numbers) in a number without a decimal are
generally not significant (see below for more details). For example, 400 has only one
significant figure (4). The trailing zeros do not count as significant.
5. Trailing zeros in a number containing a decimal point are significant. For example,
12.2300 has six significant figures: 1, 2, 2, 3, 0, and 0. The number 0.000122300 still
has only six significant figures (the zeros before the 1 are not significant). In addition,
120.00 has five significant figures since it has three trailing zeros. This convention
clarifies the precision of such numbers. For example, if a measurement that is precise
to four decimal places (0.0001) is given as 12.23, then the measurement might be
understood as having only two decimal places of precision available. Stating the result

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 as 12.2300 makes it clear that the measurement is precise to four decimal places (in
this case, six significant figures).
6. The number 0 has one significant figure. Therefore, any zeros after the decimal point
are also significant. Example: 0.00 has three significant figures.
7. Any numbers in scientific notation are considered significant. For example, 4.300 x 10-
4 has 4 significant figures.

For addition and subtraction use the following rules

1. Count the number of significant figures in the decimal portion ONLY of each number
in the problem
2. Add or subtract in the normal fashion
3. Your final answer may have no more significant figures to the right of the decimal than
the LEAST number of significant figures in any number in the problem.
4. Consider 12.346 + 102.34. If we use a calculator to evaluate this sum, we get 114.686.
The number of decimal places in our answer should be two, since the operand with
the least decimal places is 102.34, and this has two decimal places. We should
therefore round the result to two decimal places, 114.69
For multiplication and division use the following rule:
1. When multiplying or dividing, the number of significant figures in the result is equal to
the smallest number of significant figures in one of the operands. For instance, given
the following:
1.74 x 4.3)/3.42 = 2.187719 (from calculator).
The operand with the smallest number of significant figures is 4.3, so our answer
should have 2 significant figures. We therefore round 2.187719 to 2.2 to get:
1.74 x 4.3)/3.42 = 2.2 (to correct number of significant figures).

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 Chapter 2
Solution And Concentration
Solutions are defined as homogeneous mixtures that are mixed so thoroughly that neither
component can be observed independently of the other. The major component of the
solution is called solvent, and the minor component(s) are called solute. If both components
in a solution are 50%, the term solute can be assigned to either component. When a gaseous
or solid material dissolves in a liquid, the gas or solid material is called the solute. When two
liquids dissolve in each other, the major component is called the solvent and the minor
component is called the solute.

SOLUTIONS CONCENTRATION
Concentration is defined as the abundance of a constituent divided by the total volume of a
mixture. Quantitatively, the concentration of a solution describes the quantity of a solute that
is contained in a particular quantity of that solution.

Molarity
Molarity (M), is the number of moles of solute per liter of solution. This molar concentration
(ci) is calculated by dividing the moles of solute (ni) by the total volume (V).
𝑛𝑖
𝑐𝑖 =
𝑉
The SI unit for molar concentration is mol/m3. However, mol/L is a more common unit for
molarity.

Molality
Molality is an intensive property of solutions, and it is calculated as the moles of a solute
divided by the kilograms of the solvent. The molality, (m), of a solution is defined as the
amount of substance of solute in moles, nsolute, divided by the mass in kg of the solvent, msolvent
𝑛𝑠𝑜𝑙𝑢𝑡𝑒
𝑛=
𝑚𝑠𝑜𝑙𝑣𝑒𝑛𝑡

Normality
Normality, N is described as the number of gram or mole equivalents of solute present in one
litre of a solution.
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑤𝑒𝑖𝑔ℎ𝑡 (#𝐸𝑞𝑊)
𝑁=
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛𝑠 (𝐿)
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
# 𝐸𝑞𝑊 =
𝐸𝑞𝑊 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒

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 𝑀𝑜𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝐸𝑞𝑊 𝑜𝑓𝑠𝑜𝑙𝑢𝑡𝑒 =
𝐸𝑞 𝑓𝑎𝑐𝑡𝑜𝑟
𝐸𝑞𝑊 𝑓𝑎𝑐𝑡𝑜𝑟 𝑜𝑓 𝑎𝑛 𝐸𝑙𝑒𝑚𝑒𝑛𝑡 = 𝑁𝑜. 𝑣𝑎𝑙𝑒𝑛𝑐𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛
𝐸𝑞𝑊 𝑓𝑎𝑐𝑡𝑜𝑟 𝑜𝑓𝑎𝑛 𝑎𝑐𝑖𝑑 = 𝑁𝑜. 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛
𝐸𝑞𝑊 𝑓𝑎𝑐𝑡𝑜𝑟 𝑜𝑓 𝑎 𝑏𝑎𝑠𝑒 = 𝑁𝑜. 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑥𝑖𝑑𝑒
𝐸𝑞𝑊𝑓𝑎𝑐𝑡𝑜𝑟 𝑓𝑜𝑟 𝑎𝑛 𝐼𝑜𝑛𝑖𝑐 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑 = 𝑁𝑜. 𝑜𝑓 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒 𝑚𝑒𝑡𝑎𝑙
𝐸𝑞𝑊𝑓𝑎𝑐𝑡𝑜𝑟 𝑓𝑜𝑟 𝑎𝑛 𝑖𝑜𝑛 = 𝑐ℎ𝑎𝑟𝑔𝑒
𝐸𝑞𝑊𝑓𝑎𝑐𝑡𝑜𝑟 𝑜𝑓𝑜𝑥𝑖𝑑𝑖𝑧𝑖𝑛𝑔 𝑜𝑟 𝑟𝑒𝑑𝑢𝑠𝑖𝑛𝑔 𝑎𝑔𝑒𝑛𝑡 = 𝑁𝑜. 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟
𝑁 = 𝑀 𝑥 𝐸𝑞𝑊 𝑓𝑎𝑐𝑡𝑜𝑟

Example 1
Calculate the normality of 0.321 g sodium carbonate when it mixes in a 250 mL solution.
𝑆𝑜𝑑𝑖𝑢𝑚 𝑐𝑎𝑟𝑏𝑜𝑛𝑎𝑡𝑒 = 𝑁𝑎2 𝐶𝑂3 = 106 𝑔/𝑚𝑜𝑙
𝑇𝑜𝑡𝑎𝑙 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒 𝑚𝑒𝑡𝑎𝑙 = 2
Method 1
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑤𝑒𝑖𝑔ℎ𝑡 (#𝐸𝑞𝑊)
𝑁=
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛𝑠 (𝐿)
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
# 𝐸𝑞𝑊 =
𝐸𝑞𝑊 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝐹𝑜𝑟𝑚𝑢𝑙𝑎 𝑤𝑒𝑖𝑔ℎ𝑡
𝐸𝑞𝑊 𝑓𝑜𝑟 𝐼𝑜𝑛𝑖𝑐 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑 =
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒 𝑚𝑒𝑡𝑎𝑙
106 𝑔/𝑚𝑜𝑙
𝐸𝑞𝑊 𝑜𝑓𝑁𝑎2 𝐶𝑂3 = = 53
2
0.321 𝑔
# 𝐸𝑞𝑊𝑜𝑓𝑁𝑎2 𝐶𝑂3 = = 0.006
53
0.006
𝑁= = 0.02
0.25 𝐿
Method 2
𝑁 = 𝑀 𝑥 𝐸𝑞𝑊 𝑓𝑎𝑐𝑡𝑜𝑟
0.321 𝑔
𝑀𝑜𝑙𝑒 𝑜𝑓 𝑁𝑎2 𝐶𝑂3 = = 0.003 𝑚𝑜𝑙
106𝑔/𝑚𝑜𝑙
0.003 𝑚𝑜𝑙
𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦, 𝑀 = = 0.012 𝑀
0.25 𝐿

12
 𝑁 = 0.012 𝑥 2 = 0.02

Percent Concentration
Percent By Weight
Percent by mass (w/w) is the mass of solute divided by the total mass of the solution,
multiplied by 100 %.
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
%(𝑤/𝑤) = 𝑥 100
𝑡𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Example 2
What is the percent by mass of a solution that contains 26.5 g of glucose in 500 g of solution?
26.5 𝑔
%(𝑤/𝑤) = 𝑥 100 = 5.30%
500 𝑔
Percent By Volume
Percent by volume (v/v) is the volume of solute divided by the total volume of the solution,
multiplied by 100 %.
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
%(𝑣/𝑣) = 𝑥 100
𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Mass/Volume Percent
Percent by weight / volume (w/v) is the mass of solute in grams divided by the total volume
of the solution in mL, multiplied by 100 %.
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒(𝑔)
%(𝑤/𝑣) = 𝑥 100
𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛(𝑚𝐿)

Dilute Concentrations Units

Parts per Million: A concentration of a solution that contained 1 g solute and 1000000 mL
solution (same as 1 mg solute and 1 L solution)
Example 3
A solution has a concentration of 1.25 g L-1. What is its concentration in ppm?
𝑚𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑝𝑝𝑚 (𝑤/𝑣) =
𝑖𝑛 1 𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛𝑠
1.25 𝑔
1.25 𝑔𝐿−1 =
1𝐿
1000 𝑚𝑔 1
𝑝𝑝𝑚 = 1.25𝑔 𝑥 𝑥 = 1250 𝑝𝑝𝑚
1𝑔 1𝐿

13
Example 4
A solution has a concentration of 0.5 mg mL-1. What is its concentration in ppm?
0.5 𝑚𝑔
0.5 𝑚𝑔𝑚𝐿−1 =
1 𝑚𝐿
0.5 𝑚𝑔 1000 𝑚𝐿
𝑝𝑝𝑚 = 𝑥 = 500 𝑝𝑝𝑚
1 𝑚𝐿 1𝐿
Concentration Conversion
A solution contains Cu2+ ions at a concentration of 3 x 10 -4 M. What is the Cu2+ concentration
in ppm?
[𝐶𝑢2+ ] = 3 𝑥 10−4 𝑀
𝑀𝑜𝑙𝑒 𝐶𝑢2+ = 3 𝑥 10−4 𝑚𝑜𝑙
𝑉𝑜𝑙𝑢𝑚𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛𝑠 = 1 𝐿
64 𝑔 1000 𝑚𝑔
𝑚𝑔 𝑜𝑓𝐶𝑢2+ = 3 𝑥 10−4 𝑚𝑜𝑙 𝑥 𝑥 = 19.2 𝑚𝑔
1 𝑚𝑜𝑙 1𝑔
19.2 𝑚𝑔
𝑝𝑝𝑚 = = 19.2 𝑝𝑝𝑚
1𝐿
If there is 0.6 g of Pb present in 277 g of solution, what is the Pb concentration in ppm?
𝑠𝑜𝑙𝑢𝑡𝑒 (𝑚𝑔)
𝑝𝑝𝑚 (𝑤/𝑤) =
𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛𝑠 (𝑘𝑔)
0.6 𝑥 103 𝑚𝑔
𝑝𝑝𝑚 𝑃𝑏 = = 2643.2 𝑝𝑝𝑚
227 𝑥 10−3 𝑘𝑔
A throat spray is 1.40% by mass phenol, C6H5OH, in water. If the solution has a density of
0.9956 g/mL, calculate the molarity of the solution.
1.40 𝑔 𝑝ℎ𝑒𝑛𝑜𝑙
1.40 % (𝑤/𝑤) =
100 𝑔 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
1.40 𝑔
𝑀𝑜𝑙𝑒 𝑝ℎ𝑒𝑛𝑜 = = 0.015 𝑚𝑜𝑙
94 𝑔/𝑚𝑜𝑙
1 𝑚𝐿 1𝐿
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝐿) = 100𝑔 𝑥 𝑥 = 0.1 𝐿
0.9956 𝑔 1000 𝑚𝐿
0.015 𝑚𝑜𝑙
𝑚𝑜𝑙𝑎𝑟𝑖𝑡𝑦 = = 0.15 𝑚𝑜𝑙/𝐿
0.1 𝐿

14
The concentration Mg2+ ion in water is 20 ppm (w/v). What is the concentration in percentage
(w/v)?
20 𝑚𝑔
20 𝑝𝑝𝑚 =
1𝐿
20 𝑥10−3 𝑔
% 𝑤/𝑤 = 𝑥100 = 0.002 %
1000 𝑚𝐿

15
 Chapter 3
Volumetric Analysis
Volumetric analysis is a widely-used quantitative analytical method. As the name implies, this
method involves the measurement of volume of a solution of known concentration which is
used to determine the concentration of the analyte. Widely known as titration.

BASIC PRINCIPLES OF VOLUMETRIC ANALYSIS

1. The solution to be analysed contains an unknown amount of chemicals.
2. The reagent of unknown concentration reacts with a chemical of an unknown amount
in the presence of an indicator (mostly phenolphthalein) to show the end-point. It’s
the point indicating the completion of the reaction.
3. The volumes are measured by titration which completes the reaction between the
solution and reagent.
4. The volume and concentration of reagent which are used in the titration show the
amount of reagent and solution.
5. The amount of unknown chemical in the specific volume of solution is determined by
the mole fraction of the equation.

PRIMARY STANDARD
A primary standard is a measurement that is used in the calibration of working standards.
Reagent grade chemicals should be used to prepare primary standard solutions.
1. High purity
2. High stability/low reactivity
3. High equivalent weight (to reduce mass measurement error)
4. Not hygroscopic (to reduce mass changes from water absorption)
5. Non-toxic or low toxicity
6. Inexpensive
7. Readily available
There are many examples of primary standards. The most common include:
1. Sodium chloride (NaCl), which is used as a primary standard for silver nitrate (AgNO 3)
reactions.
2. Zinc powder, which can be used to standardize EDTA (ethylenediaminetetraacetic
acid) solutions after it has been dissolved in hydrochloric or sulfuric acid
3. Potassium hydrogen phthalate, or KHP, which can be used to standardize perchloric
acid and an aqueous base in an acetic acid solution.

16
Preparation of Primary Standard
Preparation of 0.05 M of KHP primary standard
1. 0.05 M means 0.05 mol of KHP in 1L solution. In 0.05 mol equivalent to 10.211 g KHP
2. Weight accurately 10.211 g of KHP and transfer it into 1000 mL volumetric flask.
3. Add distilled water to the mark.

SECONDARY STANDAED
secondary standard is a working standard - a chemical that has been standardized against a
primary standard for use in a specific analysis. In other words, a secondary standard’s
concentration is known by titrating it against a measured volume of a primary standard
instead of by weighing it out and dissolving it in a solvent. A secondary standard may be less
pure and more reactive than a primary standard, but it still upholds some of the properties of
a standard. It’s stable enough that its concentration remains known for a long time. Sodium
hydroxide (NaOH) is a common secondary standard.

Preparation of Secondary Standard

Preparation 0.1 M NaOH
1. 0.1 means 0.1 mol of NaOH in 1L solution. Containing 4.0 g NaOH
2. Weight about 4.0g NaOH and dissolve it in 1L distilled water in 1000 mL volumetric
flask.
3. Caution, the actual concentration of NaOH is not 0.1 M.
4. The exact concentration of NaOH must be determine through standardization with
KHP.

STADARDIZATION
Standardization is the process of determining the exact concentration (molarity) of a solution.
Titration is one type of analytical procedure often used in standardization. In a titration, an
exact volume of one substance is reacted with a known amount of another substance. In other
words, primary standard (known concentration) is titrated with secondary standard
(unknown concentration).
Example 1
A 0.128 g sample of KHP (HKC8H4O4) required 28.54 mL of NaOH solution to reach a
phenolphthalein endpoint. Calculate the molarity of the NaOH.
HKC8H4O4 + NaOH -----> NaKC8H4O4 + H2O
0.128 𝑔 𝐾𝐻𝑃
𝑀𝑜𝑙𝑒 𝑜𝑓 𝐾𝐻𝑃 = 𝑔 = 6.267 𝑥 10−4 𝑚𝑜𝑙
204.23 𝐾𝐻𝑃
𝑚𝑜𝑙
1 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻
𝑀𝑜𝑙𝑒 𝑁𝑎𝑂𝐻 = 6.267 𝑥 10−4 𝑚𝑜𝑙 𝐾𝐻𝑃 𝑥 = 6.267 𝑥 10−4 𝑚𝑜𝑙
1 𝑚𝑜𝑙 𝐾𝐻𝑃
6.267 𝑥 10−4 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻
𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑜𝑓 𝑁𝑎𝑂𝐻 = = 0.0220 𝑚𝑜𝑙/𝐿
0.02854 𝐿

17
ACID-BASE TITRATION
An acid-base titration is used to determines the concentration of an acid or base by exactly
neutralizing it with an acid or base of known concentration. The end of titration is indicated
by the equivalence points. Where the point at which an added titrant’s moles are
stoichiometrically equal to the moles of acid/base in the sample; the smallest amount of
titrant needed to fully neutralize or react with the analyte. The titrant is the standardized
(known) solution (either an acid or a base) that is added during titration and the analyte is the
unknown solution whose concentration is being determined in the titration
Example 2
A 20.00 mL sample of HCl was titrated with the NaOH solution from Example1. To reach the
endpoint required 23.72 mL of the NaOH. Calculate the molarity of the HCl.
HCl + NaOH -----> NaCl + H2O
𝑀𝐴 𝑉𝐴 𝑎
=
𝑀𝐵 𝑉𝐵 𝑏
1 (𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑜𝑓 𝑁𝑎𝑂𝐻)(𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑁𝑎𝑂𝐻)
𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑜𝑓 𝐻𝐶𝑙 (𝑀𝐴 ) = 𝑥
1 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐻𝐶𝑙
(0.0220 𝑀)(23.72 𝑚𝐿)
𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑜𝑓 𝐻𝐶𝑙 = = 0.0261 𝑀
20.00 𝑚𝐿

BACK TITRATION OR REVERSE TITRATION

A back titration is a titration method where the concentration of an analyte is determined by
reacting it with a known amount of excess reagent. The remaining excess reagent is then
titrated with another, second reagent. The second titration's result shows how much of the
excess reagent was used in the first titration, thus allowing the original analyte's
concentration to be calculated. A back titration may also be called an indirect titration.
Back titration is typically applied in acid-base titrations:
1. When the acid or (more commonly) base is an insoluble salt (e.g., calcium carbonate)
2. When direct titration endpoint would be hard to discern (e.g., weak acid and weak
base titration)
3. When the reaction occurs very slowly
Back (Indirect) Titration to Determine the Concentration of a Volatile Substance.
Example 3
A student was asked to determine the concentration of ammonia, a volatile substance, in a
commercially available cloudy ammonia solution used for cleaning. First the student pipetted
25.00 mL of the cloudy ammonia solution into a 250.0 mL conical flask. 50.00 mL of 0.100 mol
L-1 HCl(aq) was immediately added to the conical flask which reacted with the ammonia in
solution. The excess (unreacted) HCl was then titrated with 0.050 mol L-1 Na2CO3(aq). And

18
21.50 mL of Na2CO3(aq) was required. Calculate the concentration of the ammonia in the
cloudy ammonia solution.
1. Step 1: Determine the amount of HCl in excess from the titration results

2HCl + Na2CO3 → 2NaCl + CO2 + H2O

0.050 𝑚𝑜𝑙 1𝐿
𝑀𝑜𝑙𝑒𝑁𝑎2 𝐶𝑂3 = 𝑥 21.50 𝑚𝐿 𝑥 = 1.075 𝑥 10−3 𝑚𝑜𝑙
1𝐿 1000 𝑚𝐿
2 𝑚𝑜𝑙 𝐻𝐶𝑙
𝑀𝑜𝑙𝑒 𝐻𝐶𝑙 = 1.075 𝑥 10−3 𝑚𝑜𝑙 𝑁𝑎2 𝐶𝑂3 𝑥 = 2.150 𝑥 10−3 𝑚𝑜𝑙
1 𝑚𝑜𝑙 𝑁𝑎2 𝐶𝑂3
2. Step 2: Determine the amount of ammonia in the cloudy ammonia solution
0.100 𝑚𝑜𝑙 1𝐿
𝑀𝑜𝑙𝑒 𝐻𝐶𝑙 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑 = 𝑥 50.0 𝑚𝐿 𝑥 = 5.00 𝑥 10−3 𝑚𝑜𝑙
1𝐿 1000 𝑚𝐿
𝑀𝑜𝑙𝑒 𝐻𝐶𝐿 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑤𝑖𝑡ℎ 𝑎𝑚𝑜𝑛𝑖𝑎 = 5.00 𝑥 10−3 𝑚𝑜𝑙 − 2.150 𝑥 10−3 𝑚𝑜𝑙
= 2.580 𝑥 10−3 𝑚𝑜𝑙

HCl + NH3 → NH4Cl

1 𝑚𝑜𝑙 𝑁𝐻3
𝑀𝑜𝑙𝑒 𝑁𝐻3 = 2.580 𝑥 10−3 𝑚𝑜𝑙 𝐻𝐶𝑙 𝑥 = 2.580 𝑥 10−3 𝑚𝑜𝑙 𝑁𝐻3
1 𝑚𝑜𝑙 𝐻𝐶𝑙
2.580 𝑥 10−3 𝑚𝑜𝑙 𝑁𝐻3 1 𝑚𝐿
𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑜𝑓 𝑁𝐻3 = 𝑥 = 0.1 𝑚𝑜𝑙/𝐿
25.0 𝑚𝐿 0.001 𝐿

REDOX TITRATION
Redox titration determines the concentration of an unknown solution (analyte) that contains
an oxidizing or reducing agent. Not all titrations require an external indicator. Some titrants
can serve as their own indicators, such as when potassium permanganate is titrated against
a colourless analyte.
A common example is the redox titration of a standardized solution of potassium
permanganate (KMnO4) against an analyte containing an unknown concentration of iron (II)
ions (Fe2+).
MnO-4 + 5Fe 2+ + 8H+ → 5Fe 3+ + Mn 2+ + 2H2O
KMnO4 as a titrant can act as its own indicator; this is due to the fact that the KMnO4 solution
is bright purple, while the Fe2+ solution is colourless. It is therefore possible to see when the
titration has reached its endpoint, because the solution will remain slightly purple from the
unreacted KMnO4.
Example 4
A 1.000 g sample containing FeO and Fe2O3 plus inert material is dissolved in acid and titrated
with 0.01546 M KMnO4. If the end point volume is 17.84 mL, determine the Wt% FeO (MW
= 71.844 g/mol).

19
 𝑀𝑜𝑙𝑒 𝑀𝑛𝑂4− = (0.01546 𝑀)(0.01784 𝑚𝐿) = 2.753 𝑥 10−4 𝑚𝑜𝑙
5 𝑚𝑜𝑙 𝐹𝑒 2+
𝑀𝑜𝑙𝑒 𝐹𝑒 2+ = 2.753 𝑥 10−4 𝑚𝑜𝑙 𝑀𝑛𝑂4− 𝑥 = 1.379 𝑥 10−3 𝑚𝑜𝑙
1 𝑚𝑜𝑙 𝑀𝑛𝑂4−
1 𝑚𝑜𝑙 𝐹𝑒𝑂
𝑀𝑜𝑙𝑒 𝐹𝑒𝑂 = 1.379 𝑥 10−3 𝑚𝑜𝑙 𝐹𝑒 2+ 𝑥 = 1.379 𝑥 10−3 𝑚𝑜𝑙
1 𝑚𝑜𝑙 𝐹𝑒 2+
71.844𝑔
𝑀𝑎𝑠𝑠 𝐹𝑒𝑂 = 1.379 𝑥 10−3 𝑚𝑜𝑙 𝐹𝑒𝑂 𝑥 = 0.09908 𝑔
𝑚𝑜𝑙
0.09908 𝑔 𝐹𝑒𝑂
% 𝐹𝑒𝑂 = 𝑥 100 = 9.908 %
1.0000 𝑔 𝑠𝑎𝑚𝑝𝑙𝑒

Example 5
A second 1.000 g sample containing FeO and Fe2O3 plus inert material is dissolved in acid and
passed through a Jones reductor to reduce all of the Fe3+ to Fe2+. The resulting solution is
titrated with 0.01546 M KMnO4. If the end point volume for this sample is 28.11 mL,
determine the Wt% Fe2O3 (MW = 159.69 g/mol).
𝑀𝑜𝑙𝑒 𝑀𝑛𝑂4− = (0.01546 𝑀)(0.02811 𝑚𝐿) = 4.35 𝑥 10−4 𝑚𝑜𝑙
5 𝑚𝑜𝑙 𝐹𝑒 2+
𝑀𝑜𝑙𝑒 𝐹𝑒 2+ = 4.35 𝑥 10−4 𝑚𝑜𝑙 𝑀𝑛𝑂4− 𝑥 = 2.715 𝑥 10−3 𝑚𝑜𝑙
1 𝑚𝑜𝑙 𝑀𝑛𝑂4−
𝑀𝑜𝑙𝑒 𝐹𝑒 2+ 𝑓𝑟𝑜𝑚 𝐹𝑒2 𝑂3 = 2.715 𝑥 10−3 𝑚𝑜𝑙 − 1.379 𝑥 10−3 𝑚𝑜𝑙 = 1.336 𝑥 10−3 𝑚𝑜𝑙
𝑔
𝑀𝑎𝑠𝑠 𝐹𝑒2 𝑂3 = 1.336 𝑥 10−3 𝑚𝑜𝑙 𝑥159.69 = 0.2133 𝑔
𝑚𝑜𝑙
0.2133 𝑔
% 𝐹𝑒2 𝑂3 = 𝑥 100 = 21.33%
1.0000 𝑔 𝑠𝑎𝑚𝑝𝑙𝑒

Iodometry and Iodimetry

Iodometry and Iodimetry, Iodine is involved. Iodometry is an indirect (back) titration method
whereas iodimetry is a direct titration method.
In Iodometry, the Iodide ions get oxidized to Iodine. Then the produced Iodine is titrated with
a reducing agent such as sodium thiosulfate solution. Here, the Iodine reduces to Iodide ions
while the thiosulfate ions get oxidized further. This is the second redox reaction and it is the
reaction used for the titration. This is performed in the presence of a starch indicator to make
it easier to recognize the end point. Iodine forms a deep-blue colour complex with starch and
as the Iodine breaks down to Iodide ions, the colour disappears.
In iodimetry is a direct titration method. The analyte under investigation needs to be the
reducing agent. And this is directly titrated with a standard Iodine solution at the presence of
a suitable indicator (starch).
In iodometry, the iodine solution is made by adding iodide (I–) to iodine (I2) solutions. In the
presence of iodide, iodine reacts to form triiodide (I3–) which is highly soluble and not volatile.
I2 + I- ⇌ I3-

20
The major chemical species present in these solutions is triiodide. The reduction of triiodide
to iodide is analogous to the reduction of iodine. Triiodide reacts with thiosulfate to yield
iodide and tetrathionate
2 S2O3 2- + I3 - → S4O6 2- + 3 I -
Iodimetry, uses iodine as the titrant. Although iodine’s oxidizing power is less than that of
ceric, permanganate and dichromate ions, it is still being used because of it stability to react
rapidly with many strong reductants, and the availability of a good indicator for iodine which
is starch. Iodine also has some disadvantages. It is not very soluble in water but dissolves
readily in an iodide solution forming triiodide ion.
Example 6
1.01g of an impure sample of potassium dichromate (VI), K2Cr2O7, was dissolved in dil. sulfuric
acid and made up to 250 cm3 in a calibrated volumetric flask. A 25.0 cm3 aliquot of this
solution pipetted into a conical flask and excess potassium iodide solution and starch indicator
were added. The liberated iodine was titrated with 0.100 mol/L sodium thiosulfate and the
starch turned colourless after 20.0 mL was added. Calculate the total mass of potassium
dichromate (VI) in the original sample and hence its % purity.
2S2O32–(aq) + I2(aq) ==> S4O62–(aq) + 2I–(aq)
𝑚𝑜𝑙 1𝐿
𝑀𝑜𝑙𝑒 𝑜𝑓 𝑆2 𝑂32− = (0.100 ) 𝑥 (20.0 𝑚𝐿) 𝑥 = 0.002 𝑚𝑜𝑙
𝐿 1000 𝑚𝐿
1 𝑚𝑜𝑙 𝐼2
𝑀𝑜𝑙𝑒 𝑜𝑓 𝐼2 = 0.002 𝑚𝑜𝑙𝑆2 𝑂32− = = 0.001 𝑚𝑜𝑙
2 𝑚𝑜𝑙 𝑆2 𝑂32−
Cr2O72–(aq) + 14H+(aq) + 6I–(aq) ==> 2Cr3+(aq) + 3I2(aq) + 7H2O(l)
1 𝑚𝑜𝑙 𝐶𝑟2 𝑂72−
𝑀𝑜𝑙𝑒 𝑜𝑓 𝐶𝑟2 𝑂72− = 0.001 𝑚𝑜𝑙 𝐼2 𝑥 = 0.000333 𝑚𝑜𝑙
3 𝑚𝑜𝑙 𝐼2
1 𝑚𝑜𝑙 𝐾𝐶𝑟2 𝑂𝑂7
𝑀𝑜𝑙𝑒 𝑜𝑓𝐾𝐶𝑟2 𝑂𝑂7 = 0.000333 𝑚𝑜𝑙 𝐶𝑟2 𝑂72− 𝑥 = 0.000333 𝑚𝑜𝑙
1 𝑚𝑜𝑙 𝐶𝑟2 𝑂72−
𝑔
𝑀𝑎𝑠𝑠 𝑜𝑓𝐾𝐶𝑟2 𝑂𝑂7 𝑖𝑛 25.0 𝑚𝐿 = 0.000333 𝑚𝑜𝑙 𝑥 294.2 = 0.0980 𝑔
𝑚𝑜𝑙
𝑀𝑎𝑠𝑠 𝑜𝑓𝐾𝐶𝑟2 𝑂𝑂7 𝑖𝑛 250.0 𝑚𝐿 = 0.0980 𝑔 𝑥 10 = 0.98 𝑔
0.98 𝑔
% 𝑜𝑓 𝐾𝐶𝑟2 𝑂𝑂7 = 𝑥 100 = 97.0 %
1.01 𝑔

PERCIPITATION TITRATION
Precipitation titration is a type of titration which involves the formation of precipitate during
the titration technique. In precipitation titration, the titrant reacts with analyte and forms an
insoluble substance called precipitate.

21
Argentometric Titration
It is a type of precipitation titration which involves the use of silver ion. Symbol of silver is Ag
which is taken from its latin name argentum. Methods of Argentometric Titration are
Volhard’s Method, Fajan’s Method and Mohr’s Method
Volhard’s Method
This method involves the determination of halide (F, Cl, Br, I) ions, anions like phosphate,
chromate in acidic medium by using silver ions. This titration must be performed in acidic
medium otherwise iron ion get precipitated as hydrated oxide. Iron ion is used as indicator in
Volhard’s method. In this method first, analyte (halide ion solution or any other anionic
solution) is titrated with measured excess of AgNO3.
Cl- + Ag+ → AgCl
Then, unreacted or in excess silver ions are titrated with standard solution of KSCN using iron
ion (Fe+3) as indicator which gives red color in the end point.
Ag+ + SCN- → AgSCN
Now as the thiocyanate ion will be in excess in the titration mixture, red colour appears which
is due to formation of FeSCN(II) compound.
Fe+3 + SCN- → FeSCN+2
It is an indirect method of precipitation.
Example 7
The %w/w I– in a 0.6712 g sample was determined by a Volhard titration. After adding 50.00
mL of 0.05619 M AgNO3 and allowing the precipitate to form, the remaining silver was back
titrated with 0.05322 M KSCN, requiring 35.14 mL to reach the end point. Report the %w/w
I– in the sample.
Ag+ + SCN- → AgSCN

−
𝑚𝑜𝑙 1𝐿 1 𝑚𝑜𝑙 𝑆𝐶𝑁 −
𝑀𝑜𝑙𝑒 𝑆𝐶𝑁 𝑢𝑠𝑒𝑑 = (0.05322 ) (35.14 𝑚𝐿) ( )( )
𝐿 1000 𝑚𝐿 1 𝑚𝑜𝑙 𝐾𝑆𝐶𝑁
= 0.00187 𝑚𝑜𝑙

+
1 𝑚𝑜𝑙𝐴𝑔+−
𝑀𝑜𝑙𝑒 𝑒𝑥𝑐𝑒𝑠𝑠 𝐴𝑔 = 0.00187 𝑚𝑜𝑙 𝑆𝐶𝑁 𝑥 = 0.00187 𝑚𝑜𝑙
1 𝑚𝑜𝑙 𝑆𝐶𝑁 −
𝑚𝑜 1𝐿 1 𝑚𝑜𝑙𝐴𝑔+
𝑀𝑜𝑙𝑒 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑 𝐴𝑔+ = (0.05619 ) (50.00 𝑚𝐿) ( )( )
𝐿 1000 𝑚𝐿 1 𝑚𝑜𝑙 𝐴𝑔𝑁𝑂3
= 0.00281 𝑚𝑜𝑙
𝑀𝑜𝑙𝑒 𝐴𝑔+ 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 = 0.00281 𝑚𝑜𝑙 − 0.00187 𝑚𝑜𝑙 = 0.00094 𝑚𝑜𝑙
I- + Ag+ → AgCl

22
 − +
1 𝑚𝑜𝑙 𝐼 −
𝑀𝑜𝑙𝑒 𝑜𝑓 𝐼 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 = 0.00094 𝑚𝑜𝑙 𝐴𝑔 𝑥 = 0.00094 𝑚𝑜𝑙
1 𝑚𝑜𝑙 𝐴𝑔+
𝑔
𝑀𝑎𝑠𝑠 𝑜𝑓 𝐼 − = 0.00094 𝑚𝑜𝑙 𝑥 126.9 = 0.1192 𝑔
𝑚𝑜𝑙
0.1129 𝑔
% 𝑤/𝑤 𝑜𝑓𝐼 − = 𝑥100 = 18.29 %
0.6172 𝑔

Fajan’s Method
This method is also known as indicator adsorption method because in this method chloride
ions present in excess are adsorbed on silver chloride surface. In this method
dichlorofluorescein is used as an indicator. The end point is determined by green suspension
(of AgCl and incidation) turning pink (complex of AgCl and indicator).
Ag+ + Cl- → AgCl
Ag+ + AgCl + Indicator → AgCl-Ag+ Indicator
It is a direct method of precipitation.

Mohr’s Method
It’s a direct titration method. In this method silver nitrate is used as titrant and chloride ion
solution as analyte. Potassium chromate is used as indicator. At the end point, when all
chloride ions are consumed by silver ion, reddish brown colored precipitate is formed by
reaction of silver ion and chromate ion.
AgNO3 + Cl- → AgCl + NO3-
At the end point –
2Ag+ + CrO4-2 → Ag2CrO4
Example 8
A mixture containing only KCl and NaBr is analyzed by the Mohr method. A 0.3172-g sample
is dissolved in 50 mL of water and titrated to the Ag2CrO4 end point, requiring 36.85 mL of
0.1120 M AgNO3. A blank titration requires 0.71 mL of titrant to reach the same end point.
Report the % w/w KCl in the sample.
A blank titration is carried out by titrating a fixed and known concentration of titrant into a
solvent with zero analyte. This allows the amount of reactive substance within the plain
solvent to be determined and hence allows a determination of the error in future titration
experiments using this solvent.
𝑉𝑜𝑙𝑢𝑚𝑒 𝐴𝑔𝑁𝑂3 = 36.85 𝑚𝐿 − 0.71 𝑚𝐿 = 36.14 𝑚𝐿

+
𝑚𝑜𝑙 1𝐿 1 𝑚𝑜𝑙 𝐴𝑔+
𝑀𝑜𝑙𝑒 𝑜𝑓 𝐴𝑔 = 0.1120 𝐴𝑔𝑁𝑂3 𝑥 36.14 𝑚𝐿 𝑥 𝑥
𝐿 1000 𝑚𝐿 1 𝑚𝑜𝑙 𝐴𝑔𝑁𝑂3
= 4.048 𝑥 10−3 𝑚𝑜𝑙

23
Titrating with AgNO3 produces a precipitate of AgCl and AgBr. In forming the precipitates,
each mole of KCl consumes one mole of AgNO3 and each mole of NaBr consumes one mole
of AgNO3; thus
𝑀𝑜𝑙𝑒 𝐾𝐶𝑙 + 𝑀𝑜𝑙𝑒 𝑁𝑎𝐵𝑟 = 4.048 𝑥 10−3 𝑚𝑜𝑙
Interested in finding the mass of KCl, so let’s rewrite this equation in terms of mass.
𝑔 𝐾𝐶𝑙 𝑔 𝑁𝑎𝐵𝑟
+ = 4.048 𝑥 10−3 𝑚𝑜𝑙
74.551 𝑔/𝑚𝑜𝑙 102.89 𝑔/𝑚𝑜𝑙
Because this equation has two unknowns—g KCl and g NaBr— need another equation that
includes both unknowns.
𝑔 𝑁𝑎𝐵𝑟 = 0.3072 𝑔 − 𝑔 𝐾𝐶𝑙

𝑔 𝐾𝐶𝑙 0.3072 𝑔 − 𝑔 𝐾𝐶𝑙

𝑔 + 𝑔 = 4.048 𝑥 10−3 𝑚𝑜𝑙
74.551 102.89
𝑚𝑜𝑙 𝑚𝑜𝑙
−2 (𝑔
1.341 𝑥 10 𝐾𝐶𝑙) + 3.083 𝑥 10−2 − 9.719 𝑥 10−3 (𝑔 𝐾𝐶𝑙) = 4.048 𝑥 10−3
3.69 𝑥 10−3 (𝑔 𝐾𝐶𝑙) = 9.65 𝑥 10−4
𝑔 𝐾𝐶𝑙 = 0.262 𝑔
0.262 𝑔
%(𝑤𝑡/𝑤𝑡) 𝑜𝑓 𝐾𝐶𝑙 = 𝑥 100 = 82.6%
0.3172 𝑔

COMPLEXOMETRIC TITRATION
Complexometric titration is a form of volumetric analysis in which the formation of a colored
complex is used to indicate the end point of a titration. Complexometric titrations are
particularly useful for the determination of a mixture of different metal ions in solution. An
indicator capable of producing an unambiguous color change is usually used to detect the
end-point of the titration.
The determination of water hardness using EDTA with Eriochrome black-T as the indicator is
one example of complexometric titration. When the indicator Eriochrome Black T binds with
metal ions, it turns wine-red, however, when it is free from metal ions, it remains blue in
color. While ethylene diamine tetraacetic acid (EDTA) is colorless regardless of whether it is
coupled or not to a metal ion. As Eriochrome black T binds to metal ions, adding an EBT
indicator to the sample turns it wine-red in color. Eriochrome Black T has loosely binds with
metal ions, whereas EDTA has strongly bound with metal ions. Therefore, when all the metal
ions are bound to EDTA, the EBT indicator in the sample solution remains free and the solution
appears blue.
The reaction between a typical metal ion and EDTA (H4Y) can be written as:
M n+ + H4Y ⇌ MY (4-n)- + 4 H+

24
Metals forming stronger complexes can be titrated at lower pH values, at which the weaker
complexing metals do not react, thus selective titration of Fe3+ or Bi3+ can be carried out in
the presence of Mg2+ and Ca2+ or Pb2+, respectively at pH 1–2.
EBT (H2Ind-) indicator can be used in the titration of several cations (Mg2+, Zn2+, Cd2+). During
the determination of Mg2+, the reaction with the indicator
Mg 2+ + H!nd 2- (blue) → MgInd - (red) + H +
and then, with the titrant
MgInd – (red) + H4Y → MgY 2- + H!nd 2- (blue)

Example 9
The amount of calcium in physiological fluids can be determined by a complexometric
titration with EDTA. In one such analysis a 0.100 mL sample of a blood serum was made basic
by adding 2 drops of NaOH and titrated with 0.00119 M EDTA, requiring 0.268 mL to reach
the end point. Report the concentration of calcium in the sample as milligrams Ca per 100 mL.
𝑚𝑜𝑙 1𝑙
𝑀𝑜𝑙𝑒 𝐸𝐷𝑇𝐴 = 0.00119 𝑥 0.268 𝑚𝐿 𝑥 = 3.1892 𝑥 10−7 𝑚𝑜𝑙
𝐿 1000 𝑚𝐿
Ca 2+ + EDTA ⇌ CaEDTA 2-
1 𝑚𝑜𝑙 𝐶𝑎2+
𝑀𝑜𝑙𝑒 𝐶𝑎2+ = 3.1892 𝑥 10−7 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 𝑥 = 3.1892 𝑥 10−7 𝑚𝑜𝑙
1 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴
1000 𝑚𝑔
𝑀𝑎𝑠𝑠 𝑜𝑓𝐶𝑎2+ = 3.1892 𝑥 10−7 𝑥 40𝑔/𝑚𝑜𝑙 𝑥 = 0.01276 𝑚𝑔
1𝑔
0.01276 𝑚𝑔
% 𝑤/𝑣 𝑜𝑓 𝐶𝑎2+ = 𝑥 100 = 12.8%
0.100 𝑚𝐿
Example 10
After removing the membranes from an eggshell, the shell is dried and its mass recorded as
5.613 g. The eggshell is transferred to a 250 mL beaker and dissolved in 25 mL of 6 M HCl.
After filtering, the solution containing the dissolved eggshell is diluted to 250 mL in a
volumetric flask. A 10.00 mL aliquot is placed in a 125 mL Erlenmeyer flask and buffered to a
pH of 10. Titrating with 0.04988 M EDTA requires 44.11 mL to reach the end point. Determine
the amount of calcium in the eggshell as %w/w CaCO3.
𝑚𝑜𝑙 1𝑙
𝑀𝑜𝑙𝑒 𝐸𝐷𝑇𝐴 = 0.04900 𝑥 44.11 𝑚𝐿 𝑥 = 0.0022 𝑚𝑜𝑙
𝐿 1000 𝑚𝐿

2+
1 𝑚𝑜𝑙 𝐶𝑎2+
𝑀𝑜𝑙𝑒 𝐶𝑎 𝑖𝑛 10 𝑚𝐿 = 0.0022 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 𝑥 = 0.0022 𝑚𝑜𝑙
1 𝑚𝑜 𝐸𝐷𝑇𝐴
𝑀𝑜𝑙𝑒 𝐶𝑎2+ 𝑖𝑛 250 𝑚𝐿 = 0.0022 𝑚𝑜𝑙 𝑥 25 = 0.055 𝑚𝑜𝑙

25
 2+
1 𝑚𝑜𝑙 𝐶𝑎2+
𝑀𝑜𝑙𝑒 𝑜𝑓 𝐶𝑎𝐶𝑂3 = 0.055 𝑚𝑜𝑙 𝐶𝑎 𝑥 = 0.055 𝑚𝑜𝑙
1 𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3
𝑀𝑎𝑠𝑠 𝑜𝑓 𝐶𝑎𝐶𝑂3 = 0.055 𝑚𝑜𝑙 𝑥 100 𝑔/𝑚𝑜𝑙 = 5.5 𝑔
5.5𝑔
% 𝑤/𝑣 𝑜𝑓 𝐶𝑎𝐶𝑂3 = 𝑥 100 = 98%
5.613𝑔

26
 Chapter 4
Gravimetric Analysis
Gravimetric analysis, a method of quantitative chemical analysis in which the constituent
sought is converted into a substance (of known composition) that can be separated from the
sample and weighed. The steps commonly followed in gravimetric analysis are
1. Preparation of a solution containing a known weight of the sample,
2. Separation of the desired constituent,
3. Weighing the isolated constituent, and
4. Computation of the amount of the particular constituent in the sample from the
observed weight of the isolated substance.
The principle behind gravimetric analysis is that the mass of an ion in a pure compound can
be determined and then used to find the mass percent of the same ion in a known quantity
of an impure compound. In order for the analysis to be accurate, certain conditions must be
met:
1. The ion being analyzed must be completely precipitated.
2. The precipitate must be a pure compound.
3. The precipitate must be easily filtered.
The Gravimetric Analysis May be Classified into Four Fundamental Types:
1. Physical gravimetry or Volatilization Gravimetry also involves separating components
of the mixture by examining them by heating them or chemically decomposing them.
2. Thermogravimetry is a way of thermal analysis in which changes in physical and
chemical properties of materials are calculated as a function of increasing
temperature or as a function of time.
3. Precipitative gravimetric analysis, which uses a precipitation reaction to separate one
or more parts of a solution by incorporating it into a solid and
4. Electrodeposition or Electrogravimetry is a method which is used to separate and
quantify ions of a given substance, generally a metal.

Properties of Precipitates and Precipitating Reagents

A gravimetric precipitating agent should react specifically or at least selectively with the
analyte and give precipitates that is:
1. Enough particle size for retaining on filter paper
2. High purity (free of contaminants)
3. Low solubility that no significant loss of the analyte occurs during filtration and
washing
4. Unreactive with air (stable)
5. Known stoichiometric composition after it is dried or, if necessary, ignited.

27
Particle Size and Filterability of Precipitates
Particle size of a precipitate is influenced by
1. Precipitate solubility,
2. Temperature,
3. Reactant concentrations, and the
4. Rate at which reactants are mixed
The net effect of these variables can be accounted for, at least qualitatively, by assuming that
the particle size is related to a single property of the system called relative supersaturation,
𝑄−𝑆
𝑅𝑆𝑆 =
𝑆
Where: -
Q: the concentration of the solute at any instant
S: the concentration solute at equilibrium
Thus, when (Q - S)/S is large, the precipitate tends to be colloidal, and when (Q - S)/S is small,
a crystalline solid is more likely.

Mechanism of Precipitate Formation

Nucleation: The initial formation process in which a minimum number of atoms, ions, or
molecules join together to give a stable solid. Particle growth: The subsequent growth after
nucleation. If nucleation predominates, a precipitate containing a large number of small
particles (colloid) but if the particle growth is dominant crystalline particle is formed.
Example 1
A 3.46 g sample of limestone (CaCO3) was dissolved in 0.1M (HCl) solution according to the
following equation.
CaCO3 (s) + 2HCl (aq) => Ca2+(aq) + 2Cl -(aq) + CO2(g) + H2O (l)
Excess 0.1M (NH4)2C2O4(aq), was added to the resulting solution to precipitate the calcium
ions as calcium oxalate, CaC2O4(s). The precipitate was filtered, dried and weighed at 2.03 g.
Determine the percentage by mass of calcium in the limestone sample.
Ca2+ + C2O42- → CaC2O4
2.03 𝑔
𝑀𝑜𝑙𝑒 𝐶𝑎𝐶2 𝑂4 = = 0.0518 𝑚𝑜𝑙
128.1 𝑔/𝑚𝑜𝑙
1 𝑚𝑜𝑙 𝐶𝑎2+
𝑀𝑜𝑙𝑒 𝐶𝑎2+ = 0.0518 𝑚𝑜𝑙 𝐶𝑎𝐶2 𝑂4 𝑥 = 0.0518 𝑚𝑜𝑙
1 𝑚𝑜𝑙 𝐶𝑎𝐶2 𝑂4
𝑀𝑎𝑠𝑠 𝑜𝑓 𝐶𝑎2+ = 0.0518 𝑚𝑜𝑙 𝑥 40.1 𝑔/𝑚𝑜 = 0.364𝑔
0.364𝑔
% 𝑏𝑦 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐶𝑎2+ = 𝑥 100 = 18.3%
3.46𝑔

28
Gravimetric Factor Method
𝑔 𝑜𝑓 𝑎𝑛𝑎𝑙𝑦𝑡𝑒
𝐺𝑎𝑟𝑎𝑣𝑖𝑚𝑒𝑡𝑟𝑖𝑐 𝐹𝑎𝑐𝑡𝑜𝑟 (𝐺𝐹) =
𝑔 𝑜𝑓 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑎𝑛𝑎𝑙𝑦𝑡𝑒
𝐺𝐹 = 𝑥𝑅
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑃𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒
R = the number of mole analyte in one mole precipitate

𝑀𝑎𝑠𝑠 𝑜𝑓 𝐴𝑛𝑎𝑙𝑦𝑡𝑒 = 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑃𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒 𝑥 𝐺𝐹

Example 2
A particular water-soluble fertiliser contains phosphorus in the form of phosphate ions, PO43-
. A student used the following procedure to determine the percentage of phosphorus in a
sample of soluble fertiliser. 5.17 g of fertiliser was added to a 250.0 mL volumetric flask and
water was added to make it up to the mark. 20.00 mL of this solution was pipetted into a
conical flask. A slight excess of precipitating agent was added to precipitate the phosphate
ions as MgNH4PO4. The precipitate was filtered, washed with water and then converted by
heating into Mg2P2O7. The mass of Mg2P2O7 was 0.0312 g. Calculate the percentage by mass
of phosphate in the fertiliser.
Solution
1 𝑚𝑜𝑙
𝑀𝑜𝑙𝑒 𝑀𝑔𝑃2 𝑂7 = 0.0312 𝑔 𝑥 = 1.4 𝑥 10−4 𝑚𝑜𝑙
222.6 𝑔
2 𝑚𝑜𝑙 𝑃
𝑀𝑜𝑙𝑒 𝑃 = 1.4 𝑥 10−4 𝑚𝑜𝑙 𝑀𝑔𝑃2 𝑂7 𝑥 = 2.8 𝑥 10−4 𝑚𝑜𝑙
1 𝑚𝑜𝑙 𝑀𝑔𝑃2 𝑂7
3− −4
1 𝑚𝑜𝑙 𝑃𝑂43−
𝑀𝑜𝑙𝑒 𝑃𝑂4 = 2.8 𝑥 10 𝑚𝑜𝑙 𝑃 𝑥 = 2.8 𝑥 10−4 𝑚𝑜𝑙
1 𝑚𝑜𝑙 𝑃
94.97 𝑔
𝑀𝑎𝑠𝑠 𝑃𝑂43− 𝑖𝑛 20.00 𝑚𝑙 = 2.8 𝑥 10−4 𝑚𝑜𝑙 𝑥 = 0.027 𝑔
1 𝑚𝑜𝑙
𝑀𝑎𝑠𝑠 𝑃𝑂43− 𝑖𝑛 250.00 𝑚𝑙 = 0.027 𝑔 𝑥 12.5 = 0.33 𝑔
0.33 𝑔
% 𝑃𝑂43− = 𝑥100 = 6.38 %
5.17𝑔

Using GF
1 𝑚𝑜𝑙 𝑀𝑔𝑃2 𝑂7 ⟺ 2 𝑚𝑜𝑙 𝑃
1 𝑚𝑜𝑙 𝑃 ⟺ 1𝑚𝑜𝑙 𝑃𝑂43−
1 𝑚𝑜𝑙 𝑃𝑂43−
𝑚𝑜𝑙 𝑃𝑂43− = 2 𝑚𝑜𝑙 𝑃𝑥 = 2 𝑚𝑜𝑙 𝑃𝑂43−
1𝑚𝑜𝑙 𝑃
𝑅=2
94.97𝑔 1𝑚𝑜𝑙
𝐺𝐹 = 𝑥 𝑥 2 = 0.85
1 𝑚𝑜𝑙 222.6𝑔
𝑀𝑎𝑠𝑠 𝑃𝑂43− 𝑖𝑛 20.00 𝑚𝑙 = 0.0321 𝑔 𝑥 0.85 = 0.027𝑔
𝑀𝑎𝑠𝑠 𝑃𝑂43− 𝑖𝑛 250.00 𝑚𝑙 = 0.027 𝑔 𝑥 12.5 = 0.33 𝑔
0.33 𝑔
% 𝑃𝑂43− = 𝑥100 = 6.38 %
5.17𝑔

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Example 3

To determine the amount of magnetite, Fe3O4, in an impure ore, a 1.5419 g sample is dissolved in
concentrated HCl, giving a mixture of Fe2+ and Fe3+. After adding HNO3 to oxidize Fe2+ to Fe3+ and
diluting with water, Fe3+ is precipitated as Fe(OH)3 by adding NH3. Filtering, rinsing, and igniting the
precipitate provides 0.8525 g of pure Fe2O3. Calculate the %w/w Fe3O4 in the sample.
231.54 𝑔/𝑚𝑜𝑙 𝐹𝑒3 𝑂4 2 𝑚𝑜𝑙
𝑀𝑎𝑠𝑠 𝐹𝑒3 𝑂4 = 𝑥 = 0.82405 𝑔
159.69 𝑔/𝑚𝑜𝑙 𝐹𝑒2 𝑂3 3 𝑚𝑜𝑙
0.82405 𝑔
%𝐹𝑒3 𝑂4 = 𝑥 100 = 53.44 %
1.5419 𝑔

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 Chapter 5
Chromatography
Chromatography’ is an analytical technique commonly used for separating a mixture of
chemical substances into its individual components, so that the individual components can
be thoroughly analysed. To get the process started, the mixture is dissolved in a substance
called the mobile phase, which carries it through a second substance called the stationary
phase. The different components of the mixture travel through the stationary phase at
different speeds, causing them to separate from one another. Stationary phase does not
move with the sample whereas mobile phase moves with the sample. The nature of the
specific mobile and stationary phases determines which substances travel more quickly or
slowly, and is how they are separated. These different travel times are termed retention time.

Stationary phase Mobile phase

Stationary phase of a chromatographic Mobile phase in chromatography is a
technique is the compound used to separate compound used to separate components in
components in a mixture, but it does not a mixture, and it can move along with the
move with the components. components.
The stationary phase does not move. The mobile phase migrates through the
stationary phase.
The stationary phase is either a solid The mobile phase is either a gas or a liquid.
compound or a liquid, supported on a solid.
The stationary phase may or may not have The mobile phase completely dissolves the
interactions with the components in the sample.
sample

PLANAR CHROMATOGRAPHY
Planar chromatography is a liquid chromatography in which the stationary phase is arranged
in the form of a planar or flat bed and the mobile phase moves by capillary action. One
advantage of a planar chromatography is that multiple samples can be analysed at the same
time. This means that the conditions of chromatography can be controlled across samples
more easily if planar chromatography is used.

Paper Chromatography
Chromatography technique that uses paper sheets or strips as the adsorbent being the
stationary phase through which a solution is made to pass is called paper chromatography.
The principle involved mainly partition chromatography. Partition chromatography because
the substances are partitioned or distributed between liquid phases. The two phases are
water held in pores of the filter paper and the other phase is a mobile phase which passes
through the paper. When the mobile phase moves, the separation of the mixture takes place.

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The compounds in the mixture separate themselves based on the differences in their affinity
towards stationary and mobile phase solvents under the capillary action of pores in the paper.
Stationary phase, fine quality cellulose paper with defined porosity, high resolution, negligible
diffusion of sample and favouring good rate of movement of solvent. Mobile phase, Different
combinations of organic and inorganic solvents may be used depending on the analyte.
Example. Butanol: Acetic acid: Water (12:3:5) is suitable solvent for separating amino-acids.
Colourless analytes detected by staining with reagents such as iodine vapour, ninhydrin etc.
Or radio labelled and fluorescently labelled analytes detected by measuring radioactivity and
florescence respectively.

Rf values
The distance travelled relative to the solvent is a constant for a particular compound as long
as other parameters such as the type of paper and the exact composition of the solvent are
constant. The distance travelled relative to the solvent is called the Rf value.

𝐷𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑡𝑟𝑎𝑣𝑒𝑙𝑙𝑒𝑑 𝑏𝑦 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡

𝑅𝑓 =
𝐷𝐼𝑠𝑡𝑎𝑛𝑐𝑒 𝑡𝑟𝑎𝑣𝑒𝑙𝑙𝑒𝑑 𝑏𝑦 𝑡ℎ𝑒 𝑠𝑜𝑙𝑣𝑒𝑛𝑡
𝑎
𝑅𝑓 =
𝑏

There are various applications of paper chromatography.

1. To study the process of fermentation and ripening.
2. To check the purity of pharmaceuticals.

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 3. To inspect cosmetics.
4. To detect the adulterants.
5. To detect the contaminants in drinks and foods.
6. To examine the reaction mixtures in biochemical laboratories.
7. To determine dopes and drugs in humans and animals.
Types of paper chromatography
1. Ascending Paper Chromatography – The techniques goes with its name as the solvent
moves in an upward direction.
2. Descending Paper Chromatography – The movement of the flow of solvent due to
gravitational pull and capillary action is downwards, hence the name descending
paper chromatography.
3. Ascending – Descending Paper Chromatography – In this version of paper
chromatography, movement of solvent occurs in two directions after a particular
point. Initially, the solvent travels upwards on the paper which is folded over a rod
and after crossing the rod it continues with its travel in the downward direction.
4. Radial or Circular Paper Chromatography – The sample is deposited at the centre of
the circular filter paper. Once the spot is dried, the filter paper is tied horizontally on
a Petri dish which contains the solvent.
5. Two-Dimensional Paper Chromatography – Substances which have the same rf values
can be resolved with the help of two-dimensional paper chromatography.

Thin Layer Chromatography (TLC)

Thin Layer Chromatography is a technique used to isolate non-volatile mixtures. The
experiment is conducted on a sheet of aluminium foil, plastic, or glass which is coated with a
thin layer of adsorbent material. The material usually used is aluminium oxide, cellulose, or
silica gel. The movement occurs in such a way that the compounds which have a higher affinity
to the stationary phase move slowly while the other compounds travel fast. Therefore, the
separation of the mixture is attained. It is based on the principle of separation through
adsorption. On completion of the separation process, the individual components from the
mixture appear as spots at respective levels on the plates. Their character and nature are
identified by suitable detection techniques.

Thin Layer Chromatography Applications

1. The qualitative testing of Various medicines such as sedatives, local anaesthetics,
anticonvulsant tranquilisers, analgesics, antihistamines, steroids, hypnotics is done by
TLC.

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 2. TLC is extremely useful in Biochemical analysis such as separation or isolation of
biochemical metabolites from its blood plasma, urine, body fluids, serum, etc.
3. Thin layer chromatography can be used to identify natural products like essential oils
or volatile oil, fixed oil, glycosides, waxes, alkaloids, etc.
4. It is widely used in separating multicomponent pharmaceutical formulations.
5. It is used to purify of any sample and direct comparison is done between the sample
and the authentic sample.
6. It is used in the food industry, to separate and identify colours, sweetening agent, and
preservatives.
7. It is used in the cosmetic industry.
8. It is used to study if a reaction is complete.

COLUMN CHROMATOGRAPHY
In column chromatography, the stationary phase, a solid adsorbent, is placed in a vertical
glass (usually) column. The mobile phase, a liquid, is added to the top and flows down through
the column by either gravity or external pressure.
The mixture to be analysed by column chromatography is placed inside the top of the column.
The liquid solvent (the eluent) is passed through the column by gravity or by the application
of air pressure. An equilibrium is established between the solute adsorbed on the adsorbent
and the eluting solvent flowing down through the column. Because the different components
in the mixture have different interactions with the stationary and mobile phases, they will be
carried along with the mobile phase to varying degrees and a separation will be achieved. The
individual components, or elutants, are collected as the solvent drips from the bottom of the
column.

Term Definition
Mobile phase or carrier solvent moving through the column
Stationary phase or substance that stays fixed inside the column
adsorbent
Eluent fluid entering the column
Eluate fluid exiting the column (that is collected in flasks)
Elution the process of washing out a compound through a column using a
suitable solvent
Analyte mixture whose individual components have to be separated and
analysed

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The two most common examples of stationary phases for column chromatography are silica
gel and alumina while organic solvents are regarded as the most common mobile phases. The
polarity of the solvent which is passed through the column affects the relative rates at which
compounds move through the column. Polar solvents can more effectively compete with the
polar molecules of a mixture. If a solvent is not polar enough, no compounds will elute from
the column. Proper choice of an eluting solvent is thus crucial to the successful application of
column chromatography as a separation technique.
Often a series of increasingly polar solvent systems are used to elute a column. A less-polar
solvent is first used to elute a less-polar compound. Once the less-polar compound is off the
column, a more-polar solvent is added to the column to elute the more-polar compound.
If the compounds separated in a column chromatography procedure are coloured, the
progress of the separation can simply be monitored visually. More commonly, the compounds
to be isolated from column chromatography are colourless. In this case, small fractions of the
eluent are collected sequentially in labelled tubes and the composition of each fraction is
analysed.

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