Chapter One

Introduction
to Analytical
Chemistry
Prepared by: Medhanie
G. 1
 Definition of Analytical
Chemistry
Analytical chemistry is the branch of chemistry
that deals with:

 Separation, Identification and Determination

of components in a given sample.

 It also includes coverage of chemical

equilibrium and statistical evaluation of the
data.
2
 Classification of Analytical Chemistry
Analytical chemistry can be broken down into two
general areas of chemical analysis:
•Qualitative Analysis: Attempting to identify what materials are
present in a given sample.
•Quantitative Analysis: Determining how much of a material is
present in a given sample.
• this means it provides numerical information of the
sample.
►Note that: a complete chemical analysis of a given
sample includes both qualitative and quantitative
determinations.
3
 What do we mean by a chemical measurement?

Chemical measurements determine the chemical composition of

materials that may be made up of many compounds.
Qualitative measurements describe the identity of the
components and quantitative measurements find the
concentrations of specific components.
An example of a qualitative measurement would be
to identify the plastic that was used to make a bottle.
Typical quantitative measurements would be to
measure the amount of active drug in a tablet in
milligrams or the concentration of lead in drinking water
or soil in ppm.
4
 The Role of Analytical Chemistry
Analytical chemists work to improve the reliability of
existing techniques to meet the demands for better chemical
measurements which arise usually in our world.
It is versatile interdisciplinary and it has a wide
application in :
Medicine
Industry
Environmental
Food and Agriculture
Forensics
Archaeology etc…

5
Consider a few examples:

The concentrations of oxygen and carbon dioxide are

determined in millions of blood samples every day and used
to diagnose and treat illnesses.
Quantities of hydrocarbons, nitrogen oxides and carbon
monoxide present in automobile exhaust gases are measured
to assess the effectiveness of smog-control devices.
Quantitative measurements of ionized calcium in blood
serum help to diagnose parathyroid disease in humans.
Quantitative determination of nitrogen in foods establishes
their protein content and thus their nutritional value.

6
 Instrumental and Non-instrumental Methods
Classical measurements (non-instrumental methods) are based
on adding reagents to cause a precipitate or a color change that can
be observed directly.

One can determine concentrations by titration with

standard solutions using an indicator that changes color, or
by weighing a precipitate and identify compounds by
measuring the melting or boiling points.
Nowadays the vast majority of chemical measurements are made
by instrumental methods.
The reasons include that instrumental methods are much
more sensitive, more precise, require less time &
reagent for analysis, can be automated to run
continuously, allow measurements outside the laboratory,
7
etc.
 Analytical Methodology
1. Understanding and defining the problem

2. History of the sample and background of the problem

3. Plan of action and execution

4. Analysis and reporting of results

8
1. Understanding and Defining the Problem
• What accuracy is required?
• Is there a time (or money) limit?
• How much sample is available?
• How many samples are to be analyzed?
• What is the concentration range of the analyte?
• What components of the system will cause an interference?
•What are the physical & chemical properties of the sample
matrix?

2. History of sample and background of the problem

•Background info can originate from many sources:
• The client, competitor’s products
• Literature searches on related systems
•Sample histories; how sample was collected, transported,
stored and the sampling process
9
3. Plan of Action
Performance Characteristics: Figures of Merit
• Which analytical method should I choose? How good is the
meas’t,
• How reproducible is it? Precision
• How close to the true value is it? Accuracy/Bias
• How small of a difference can be measured? Sensitivity
• What concentration/mass/amount/range? Dynamic Range
• How much interference? Selectivity
4. Analyzing and Reporting Results
No work is complete until the “customer” is HAPPY!
• Analytical data analysis takes many forms: statistics,
chemometrics, simulations, etc…
•Analytical work can result in:
•peer-reviewed papers, etc…
•technical reports, lab notebook records, etc...
10
 Components of Analytical Methods
Obtain and store sample

Extract data Pretreat and prepare sample

from sample
Perform measurement
(instrumentation)

Compare results
with standards
Apply required After reviewing
Covert data statistical techniques results
into information
Verify results
might be
necessary
Transform
information into
to modify and
Present information repeat
knowledge
procedure 11
Basic Equipments
Instruments for:
measuring mass:---------------------------
Volume :------------------------------------------------
Drying sample:------------------------------------------
The Laboratory Note Book
Important terminologies / languages in analytical
chemistry
Sample, analyte, Matrix
Sampling ?
Steps in sample handling

Steps in sample
preparation
Sample preservation
Homogenization
Extraction
Concentration
Clean up
Calibration
the process of insuring the instrument/ equipment
used to measure the signal is operating correctly by
using a standard known to produce exact signals.

Standardization
the process of experimentally determining the
relation between the signal and the analyte.
Chapter
Two
2. Statistical
Evaluation of 15
 A single measurement can not be taken as an accurate result.

Our confidence in an analytical result is increased by increasing

the number of parallel determinations, known as replicate
determinations.

That is, the more numerous the number of observations the more
their results approach the truth value.
The replications are useful to us in two ways.
First, a reliable central value of the set of analytical data will
be evaluated, which is mean.
Second, an analysis of the variation in results helps us to
estimate the uncertainty associated with the central value of
the data.
16
 2.1. Mean, Median, Standard Deviation, Variance
Mean: is simply the sum of replicate measurements divided by the
number of measurements in the set.
 The mean is the most widely used measure of the central value.
 For a finite sample (for n < 30) the mean known as sample
mean.

 For the number of observations approaching infinity, the mean

known as population mean, μ.

17
Median
 is the middle value when we order our data from the smallest to
the largest value.
 When the data set includes an odd number of entries, the
median is the middle value.
For an even number of entries, the median is the average of the
n/2 and the (n/2) + 1 values, where n is the size of the data set.

Mode
 The observation which occurs most frequently (i.e. with
maximum frequency) in a series of observations is known as mode.

Range
 The difference between the largest and smallest values in a set of
measurements is known as the range.
It tells the spread of data.
18
Example: The result from six replicates determinations of iron (in
ppm) are: 19.4, 19.5, 19.6, 19.8, 20.1, 20.3

Therefore,
Mean = Xm = (19.4+19.5+19.6+19.8+20.1+20.3)/6 = 19.78 ppm
Median = (19.6+19.8) / 2 = 19.7 ppm
Note: In analytical chemistry, the mean or average is most of the
times considered as the most probable value.

Deviation
The difference between a particular measured value
(observation) and the arithmetical mean of a series of
measurements and this difference is called as its deviation for
apparent error.
19
Standard Deviation (s)
Describes the spread of a data set’s individual values about its
mean.
And used to indicate the precision of an analysis.

(N )

(n < 30)

20
21
Variance (V)
This is the square of the standard deviation.

Relative Standard Deviation (RSD) or Coefficient of

Variation (CV)
RSD is calculated by dividing the standard deviation by the
mean value of the analytical data.

22
 Types and Sources of Error
There are many causes of error that make results differ from the
true value.
It is important to know how good our measurements are.
For example: is the material pure or contaminated, or
what is the uncertainty in a measured concentration?

There is random or indeterminate error that causes results to

vary when we repeat measurements.
Random errors will cause results sometimes to be too
high and sometimes to be too low.
There are also systematic or determinate errors which cause
all our results to be too high or all of them to be too low.
When there are systematic errors we say that there is a
bias in the results.
23
 Gross Errors
Most gross errors are personal and are attributable to
carelessness, laziness, or ineptitude.
Usually obvious - give “outlier” readings.
Detectable by carrying out sufficient replicate
measurements.

Examples: would include a complete instrument breakdown,

accidentally dropping or discarding a crucial sample, or
discovering during the course of the experiment that a
supposedly pure reagent was in fact badly contaminated.

24
 Examples: incorrectly calibrated
instrument, such as a burette,
balance or pH meter, an impurity
in a reagent, a side reaction in a
titration, and heating a sample at
too high temperature.

Can be estimated using

replicate measurements.
 Can be minimized by good
technique but can not be
eliminated
 reflected by its precision.
25
 Main Characteristics of a Chemical Measurement:
a.Accuracy – is the measure of how close the result obtained is to
the ‘true’ value. One can define accuracy as an average value of the
difference between the observed result and the true value and it is
affected by both random and systematic errors.

Where: there are N measurements, Si is

the Ith result and Si(true)is the true result.

b. Precision – is the measure of the variation between repeated

measurements. The precision is typically quoted as the standard
deviation of repeated results.

Where: Si is the ith result and

Sav is the mean of all results.
26
Illustrating the difference between “accuracy” and “precision”

Low accuracy, Low precision Low accuracy, High precision

High accuracy, low precision High accuracy, High precision

c. Sensitivity – is the ability to measure small changes in
concentration. It is defined as the ratio of the change in response
to the change in concentration and is the slope of a plot of
response against concentration.
Where: S is the response, c is the
S  S bl
m concentration and Sbl is the response
c for a blank solution with c=0.

d. Selectivity – refers to the ability to measure on species in the

presence of another. It is expressed as the ratio of the sensitivities
of the measurement for the two species.

mA
S Where: mA and mB are the sensitivities
mB of species A and B, respectively
28
 2.4. Confidence Intervals
 In most of the situation encountered in chemical analysis, the true
value of the mean,  ,can not be determined because a huge number
of measurements (approaching infinity) would be required.

 However, with statistics we can establish an interval

surrounding an experimentally determined sample mean, x ,
within which the population mean,  , is expected to lie with a
certain degree of confidence based on probability distribution.

 Thus, the range (or a numerical interval) around the sample mean
of a set of replicate analytical results within which the population
mean, μ, can be expected to lie, with a certain degree of confidence
(i.e., with a certain probability), is known as Confidence Interval.
29
The boundaries of this range are called the Confidence Limits.
The probability or possibility that the true value falls within the
range is called the Probability or Confidence Level.

Consider the example that in a set of iron determination it is 95%

probable that the population mean, μ, lies in the limit ± 0.20% Fe
x
of sample mean = 11.30% Fe.
It tells that the confidence interval is 11.10% to 11.50% Fe
with 95% probability.

The 95% confidence limit for μ = 11.30% ±0.20% Fe, and

the confidence level is 95%.

30
i. Confidence limits of the mean for large samples
For large samples, the confidence limits of the mean are given
by:
CL for   x  zs
N
As the sample size gets larger, s becomes more reliable as an
estimate of σ (popn standard deviation).
Where the value of z depends on
the degree of confidence required.
50% of area lies between 0.67s
80% “ 1.29s
90% “ 1.64s
95% “ 1.96s
99% “ 2.58s

31
Example: Measurements of glucose levels in a patient suffering
from diabetes gave the following results: 1.108, 1.100, 1.122,
1.088, 1.115, 1.099 and 1.075 g/L. Calculate the 95% confidence
interval when s = 0.019 g/L.
1.108  1.100  1.122  1.088  1.115  1.099  1.075
x = 1.101 g/L
7

CL for   x  zs , CL for   1.101  1.96 x 0.019

N 7

μ = (1.101 ± 0.014) g/L with 95% confidence

Thus, it is 95% probable that the population mean

lies in the interval from 1.087 to 1.115 g/L.
32
 ii. Confidence limits of the mean for small samples
As the sample size gets smaller, s becomes less reliable as an
estimate of σ. __
t s
X n 1

n
Table 1: Values of t for the listed confidence interval
Values of t for confidence interval of
Degrees of freedom 80% 90% 95% 99%
1 3.08 6.31 12.7 63.7
2 1.89 2.92 4.30 9.92
3 1.64 2.35 3.18 5.84
4 1.53 2.13 2.78 4.60
5 1.48 2.02 2.57 4.03
6 1.44 1.94 2.45 3.71
7 1.42 1.90 2.36 3.50
8 1.40 1.86 2.31 3.36
9 1.38 1.83 2.26 3.25 33
Example: The sodium ion content of a urine specimen was
determined by using an ion-selective electrode. The following
values were obtained: 102, 97, 99, 98, 101, 106 mM. What are the
95% and 99% confidence limits for the sodium ion concentration?
• The mean and standard deviation of these values are 100.5
mM and 3.27 mM respectively. There are six measurements and
therefore 5 df.
 t5 for 95% confidence limits is 2.57 and the 95% confidence limits
of the mean are given by:
2.57 x3.27
100.5   100.5  3.4mM
6
Similarly the 99% (4.03) confidence limits are given by:

4.03x3.27
100.5   100.5  5.4mM
6
34
 2.5. Testing for Significance
In analytical chemistry we develop new methods of analysis and
it is frequently desired to compare the results of a new method with
those of an accepted method (e.g.; from the National Institute of
Standards and Technology, NIST).

The average values obtained from the two methods may show a
difference. The question arises whether this difference is due to
random fluctuation (indeterminate error) or systematic error
(directional fluctuation).

The answer is qualified by a degree of certainty involving the

method what is known as Null Hypothesis which considers that
there is no significant difference between two sets of data.
35
In null hypothesis procedure a comparison of statistical
parameters (based on mean or standard deviation, or
other), is made between two sets of replicate
measurements obtained by two different methods.

With this comparison the value of the statistical parameter

of test of significance is calculated and compared with the
value of the parameter given in the statistical tables
available.

36
A simple examination of the two values (calculated &
tabular) will show how large a difference needs to be in
order to be considered for the limit of significant divergence.

Thus, if there is not a statistically significant divergence,

means the null hypothesis is valid or that there is no
source of systematic error and the variation in results
follows the law of random errors.

And if there is a statistically significant divergence,

means the null hypothesis is not valid & a source of
systematic error is highly probable.

37
 Comparison of an Experimental mean with a known value
The t-test is used to test the null hypothesis that two means do
not differ significantly.
(x   ) n
t 
s
i) If tcalc < ttab, the null hypothesis is valid, there is no significant
difference between the two means ( x and μ), the variation in results
is just by random errors and no systematic source of error is
probable.
ii) If tcalc > ttab, then the null hypothesis is incorrect, a significant
difference between the two means is indicated and the difference is
due to some source of systematic error in the values of finite series.
Therefore, the smaller the calculated t value, the more confident
you are that there is no significant difference between the two
means. 38
Table 2: values of t for various levels of probability
Degrees of Factor for confidence interval
Freedom 80% 90% 95% 99% 99.9%

1 3.08 6.31 12.7 63.7 63.7

2 1.89 2.92 4.30 9.92 37.6
3 1.64 2.35 3.18 5.84 12.9
4 1.53 2.13 2.78 4.60 8.60
5 1.48 2.02 2.57 4.03 6.86
6 1.44 1.94 2.45 3.71 5.96
7 1.20 1.90 2.36 3.50 5.40
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
11 1.36 1.80 2.20 3.11 4.44
12 1.36 1.78 2.18 3.06 4.32
13 1.35 1.77 2.16 3.01 4.22
39
14 1.34 1.76 2.14 2.98 4.14
Example 1: In a new method for determining calcium in water, the
following values were obtained for tap water samples spiked with
50 g ml−1 of calcium:
50.4, 50.7, 49.1, 49.0, 51.1 g/ml
Is there any evidence of systematic error?

Solution: mean= 50.06 g/ml and Standard deviation= 0.956 g/ml

(50.06  50 ) 5
tcal   0.14
0.956
From the above table, the critical value is t4 = 2.78 (P = 0.05).
Since the observed value of tcal is less than the critical value, ttab
the null hypothesis is retained: there is no evidence of
systematic error.
40
 F-test
(for the Comparison of Standard Deviations)
In many cases it is also important to compare the standard
deviations, i.e. the Random errors of two sets of data.
The F-test serves to show whether the precision of two
different methods is the same within specified probability limits.
It is applied in terms of variance ratio.

The F value which is the ratio of two variances in question is

determined by the relation placing of the larger of the two
variances in numerator so that the value of F is always greater
than one. 41
 To test null hypothesis for the two sets of data by F test:

i.If Fcalc < Ftab, then no statistically significant difference

is indicated between s1 and s2 (i.e. between two sets of
data), and the null hypothesis is valid, and

ii.If Fcalc > Ftab, then s1 is significantly greater than s2, and
the null hypothesis is not valid.

42
Table 3: F-values at the 95% probability level

n-1 for larger S2

n-1 for smaller S2 3 4 5 6 10 20

3 9.28 9.12 9.01 8.94 8.79 8.66

4 6.59 6.39 6.26 6.16 5.96 5.80
5 5.41 5.19 5.05 4.95 4.74 4.56
6 4.76 4.53 4.39 4.28 4.06 3.87
10 3.71 3.48 3.33 3.22 2.98 2.77
20 3.10 2.87 2.71 2.60 2.35 2.12

43
Example: Two students have a contest to see who is the more
precise analyst. John makes seven determinations of the percentage
of toluene in benzene, and Mary make five. The results are:
1 2 3 4 5 6 7
John 21.5 22.2 21.4 21.6 22.0 21.4 22.0
Mary 21.8 21.5 21.3 21.6 21.5 - -
Determine the significance of the two precisions.
X John= 21.7 X Marry= 21.5
SJohn = 0.33 SMarry = 0.19

2
Solution: F S John

(0.33) 2
 3.02
2 2
S Marry
(0.19)

 The table value (6 and 4 degrees of freedom) is 6.16, so the

difference is not significant at the 95% level.
44
 2.6. Rejection test or the Q-test
Every experimentalist is familiar with the situation in which one
(or possibly more) of a set of results appears to differ
unreasonably from the others in the set. Such a measurement is
called an outlier.
The Q test is a simple, widely used statistical test for deciding
whether a suspected result should be retained or rejected.
/ suspect  nearest /
Q
(highest  lowest )
If the calculated value of Q exceeds the critical
value, the suspect value is rejected.

45
 Table 4: Critical values for Rejection quotient Q

Number of Q crit (Reject if Q exp > Q crit)

observations 90% 95% 99%

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

46
Example: If three further measurements were added to those
given in the example above so that the complete results became:
0.403, 0.410, 0.401, 0.380, 0.400, 0.413, 0.408
should 0.380 still be retained (CL=95%)?

/ suspect  nearest /
Solution: Q
( highest  lowest )

/ 0.380  0.400 /
Q  0.606
(0.413  0.380)
The critical value of Q (P = 0.05) for a sample size 7 is
0.570. The suspect value, 0.380, is rejected.
47
 Chapter Three
3. Solutions and
their
Concentrations
48
Concentration of Solution

Solvent Solute

49
 Solution Formation
• Solute
Dissolved substance, or the substance in a smaller quantity
• Solvent
Liquid dissolved in, or the substance in a larger quantity
• Saturated solution
Contains the maximum amount of solute that will dissolve in a
given solvent.
• Unsaturated
Contains less solute than a solvent has the capacity to dissolve.
• Supersaturated
Contains more solute than would be present in a saturated
solution.
• Crystallization
The process in which dissolved solute comes out of the
solution and forms crystals. 50
 Concentration of Solution
Moles of solute Mol
Molarity (M)= =
Liter of solution L
Mole Fraction(c) = Moles of solute
Total moles of solution
Moles of solute = Mol
Molality(m) =
Kilograms of solvent Kg
No. of equivalents of solute
Normality (N) =
Volume of solution (L)
No. Equivalents = Actual mass / Equivalent weight
Equivalents wt. = Molar mass / Total no of positive charges
52
 Molarity

NaCl Molarity Example Problem 1

12.6 g of NaCl are dissolved in water making

344mL of solution. Calculate the molar
concentration.

 1molNaCl 
12.6 g NaCl  
moles solute  58.44 gNaCl 
M= =
L solution  1L 
344 mL   solution
 1000mL 
= 0.627 M NaCl
53
 Molarity

NaCl Molarity Example Problem 2

How many moles of NaCl are contained in 250 mL of
solution with a concentration of 1.25 M?

moles solute therefore the

M= solution contains
L solution
 1L  1.25 mol NaCl
250. mL   = 0.250 L solution
 1000mL  1 L solution
Volume x concentration = moles solute
 1.25 mol NaCl 
0.250 L solution   = 0.313 mol NaCl
 1 L solution  54
 Molarity

NaCl Molarity Example Problem 3

What volume of solution will contain 15 g of NaCl if
the solution concentration is 0.75 M?

moles solute therefore the

M= solution contains
L solution
 1 mol NaCl  0.75 mol NaCl
15 g NaCl   = 0.257 mol
 58.44 g NaCl  1 L solution
moles solute ÷ concentration = volume solution
 1 L solution 
0.257 mol NaCl   = 0.34 L solution
 0.75 mol NaCl  55
 % Concentration
mass solute
% (w/w) = x 100
mass solution

mass solute
% (w/v) = volume solution x 100

volume solute
x 100
% (v/v) = volume solution
Mass and volume units must match.
(g & mL) or (Kg & L)
56
 % Concentration
Example Problem 1
What is the concentration in %w/v of a solution containing 39.2 g of
potassium nitrate in 177 mL of solution?
mass solute 39.2 g
% (w/v) =  100  100 = 22.1 % w/v
volume solution 177 mL

Example Problem 2
What is the concentration in %v/v of a solution containing 3.2 L of
ethanol in 6.5 L of solution?
volume solute 3.2 L
% (v/v) =  100  100 = 49 % v/v
volume solution 6.5 L
57
 % Concentration
Example Problem 3
What volume of 1.85 %w/v solution is needed to
provide 5.7 g of solute?
1.85 g solute
% (w/v) =
100 mL solution
We know: We want to get:
g solute
g solute and mL solution
mL solution

 100 mL solution 
5.7 g solute   = 310 mL Solution
 1.85 g solute 
g solute ÷ concentration = volume solution

58
 Parts per million/billion (ppm & ppb)

mass solute mg
ppm = × 106 or = ppm
volume solution L
mass solute g
ppb = × 109 or = ppb
volume solution L

AND
Mass and volume units must match.
For very low
(g & mL) or (Kg & L) concentrations:
ng
parts per trillion = ppt
L 59
 ppm & ppb
Example Problem 1
An Olympic sized swimming pool contains
2,500,000 L of water. If 1 tsp of salt
(NaCl) is dissolved in the pool, what is the
concentration in ppm?
1 teaspoon = 6.75 g NaCl
or
g solute mg solute
ppm = ×106 ppm =
mL solution L solution

6.75 g 6 6.75 g  1000

1 g 
mg
ppm = ×10 ppm =
2.5×106 L  1000
1 L 
mL
2.5×106 L

ppm = 0.0027 ppm = 0.0027

60
 ppm & ppb
Example Problem 2
An Olympic sized swimming pool contains
2,500,000 L of water. If 1 tsp of salt
(NaCl) is dissolved in the pool, what is the
concentration in ppb?
1 teaspoon = 6.75 g NaCl
or
g solute  g solute
ppb = ×109 ppb =
mL solution L solution

ppb =
6.75 g
×10 9
ppb =
6.75 g  106 mg
1 g 
2.5×106 L  1000
1 L 
mL
2.5×106 L
ppb = 2.7 ppb = 2.7
61
 Mole Fraction
B A B A
A A A
A A A B
B B B A
B A
A A A A B

Mole Fraction (c)

moles of A A
c A = sum of moles of all components A + B

moles of B B
c B = sum of moles of all components A + B

Since A + B make up the

entire mixture, their mole
fractions will add up to one.
 A  B  1.00 62
 Mole Fraction
Example Problem 1
In our glass of iced tea, we have added 3 tbsp of
sugar (C12H22O11). The volume of the tea (water)
is 325 mL. What is the mole fraction of the
sugar in the tea solution?
(1 tbsp sugar ≈ 25 g)
First, we find the moles of both the
solute and the solvent.
 1 mol C12 H 22 O11   1 mol H 2 O 
75.g C12 H 22O11   = 0.219 mol 325mL H 2 O   = 18.1 mol
 342 g C12 H 22 O11   18.0 g H 2
O 
Next, we substitute the moles of both into the mole fraction equation.

χ sugar =
moles solute
total moles solution
=
0.219 mol sugar
(0.219 mol + 18.1 mol)
 0.012
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 Mole Fraction
Example Problem 2
Air is about 78% N2, 21% O2, and 0.90% Ar.
What is the mole fraction of each gas?
First, we find the moles of each gas. We assume 100.
grams total and change each % into grams.
 1 mol N 2   1 mol O 2 
78g N 2   = 2.79 mol 21g O 2   = 0.656 mol
 28 g N 2   32 g O 2 
 1 mol Ar  Next, we substitute the moles of each into
0.90g Ar   = 0.0225 mol
 40. g Ar  the mole fraction equation.

χ =
moles N 2
N2 total moles χ =
moles O 2
O2 total moles χ Ar =
moles Ar
total moles
2.79 mol N 2 0.656 mol O 2 0.0225 mol Ar
= = =
(2.79 + 0.656 + 0.0225) (2.79 + 0.656 + 0.0225) (2.79 + 0.656 + 0.0225)

 0.804  0.189  0.00649 64

 Molal (m)
Example Problem 1
If the cooling system in your
car has a capacity of 14 qts, and
you want the coolant to be protected from freezing down
to -25°F, the label says to combine 6 quarts of antifreeze
with 8 quarts of water. What is the molal
concentration of the antifreeze in the mixture?
mol solute antifreeze is ethylene glycol C2H6O2
m=
Kg solvent 1 qt antifreeze = 1053 grams
1 qt water = 946 grams
 1053 g C2 H 6O 2   1mol C2 H 6O 2 
6 Qts    62.1 g C H O 
 1 Qt C H O
2 6 2   2 6 2 
m= = 13 m
 946 g H 2O   1 Kg 
8 Qts    
 1 Qt H 2 O   1000 g 
 Normality (N)
Example 1: - Calculate the normality of a solution containing 3.65 g
of HCl per 0.500 L of solution. The mass of an equivalent of HCl is
36.5 g.
Solution

•No of equivalents of HCl = 3.65g HCl/(36.5g HCl /1+ (equivalents))

= 0.1 equivalents

•Normality =No. of equivalents / Volume of solution

= 0.1 equiv. / 0.5 L = 0.2 equiv. L-1

= 0.2 N

66
Steps involved in preparing solutions
from pure solids

67
Steps involved in preparing solutions
from pure solids
Calculate the amount of solid required
Weigh out the solid
Place in an appropriate volumetric flask
Fill flask about half full with water and mix.
Fill to the mark with water and invert to mix.

You should be able to describe this process

(including calculating the mass of solid to use) for
any solution I specify.

68
 Dilutions
Many laboratory chemicals such as acids are purchased
as concentrated solutions (stock solutions).
e.g. 12 M HCl
12 M H2SO4

More dilute solutions are prepared by taking a certain

quantity of the stock solution and diluting it with water.

69
 Dilutions
A given volume of a stock solution contains a specific number
of moles of solute.
e.g.: 25 mL of 6.0 M HCl contains 0.15 mol HCl
(How do you know this???)
25 mL HCl 25 mL H2O 50 mL

0.15 mol + = 0.15 mol

If 25 mL of 6.0 M HCl is diluted with 25 mL of water, the

number of moles of HCl present does not change.
Still contains 0.15 mol HCl.
70
 Dilution Calculation
When a solution is diluted, the concentration of the
new solution can be found using:
Mc x V c = M d x V d

Where :
Mc= initial concentration (mol/L)= more concentrated
Vc = initial volume of more conc. solution
Md = final concentration (mol/L) in dilution
Vd = final volume of diluted solution

71
 Dilution Calculation
Example 1: What is the concentration of a solution
prepared by diluting 25.0 mL of 6.00 M HCl to a total
volume of 50.0 mL?
Given: Vc = 25.0 mL
Note: Vcand Vd do not have to be
Mc = 6.00 M in liters, but they must
Vd = 50.0 mL be in the same units.

Find: Md = ???
Use Vcx Mc= Vdx Md
Solve for Md
Md = 3.00 M
72
 Dilution
Make a diluted solution once you know Vc and Vd
Use a pipette to deliver a volume of the concentrated
solution to a new volumetric flask.
Add solvent to the line on the neck of the new flask.
Mix well.

73
 Practice
1. How many mL of 5.0 M K2Cr2O7 solution must be diluted
to prepare 250 mL of 0.10 M solution?

Vc = ? Mc = 5.0M Vd = 250 mL Md = 0.10M

2. If 10.0 mL of a 10.0 M stock solution of NaOH is diluted

to 250 mL, what is the concentration of the resulting
solution?
Md = ? Vc = 10.0 mL Mc = 10.0M Vd = 250 mL

74