GENERAL CHEMISTRY

Laboratory Manual

(CHEM 107)

Middle East Technical University,

Department of Chemistry

ANKARA
 PREFACE
This Laboratory manual is prepared by the teaching staff of General Chemistry courses and will
be useful for freshman chemistry students who take General Chemistry I (Chem 101, Chem
111, and Chem 107) and General Chemistry II(Chem 102 and Chem 112) courses in the Middle
East Technical University at Chemistry Department.

The experiments are selected to show some basic techniques and proceures by which a chemist
obtains information by the experiments, and then uses the data collected to draw conclusions
about properties and behavior of matter. All the experiments have introduction sections giving
background information needed to bridge the gap between lecture presentations of the topics
and laboratory studies.

All rights reserved. No parts of this book may be reproduced in any form or by any means,
including photocopying, recording, or other electronic or mechanical methods.

10
GENERAL CHEMISTRY LABORATORY EXPERIMENTS

CHEM 107 EXPERIMENTS

1. Introductory Laboratory Techniques

2. The Law of Definite Proportions
3. Enthalpy of Formation
4. Solutions
5. Colligative Properties
6. Electrochemistry-Voltaic cells

11
 Some Laboratory Equipments

Beaker Volumetric Erlenmayer Round Graduated Burette

flask Flask Bottom Cylinder
Florence

Pi-pump
Dropper

Thermometer Pipette Funnel Wash Bottle Test Tube UV-cell

Crucible Stirring Rod spatula

Clamp Toggle

Watch Glass

Test Tube
Universal Bunsen Tripod Wire Gauze Holder
Stand Burner

12
13
 Introductory
Introductory Laboratory
Laboratory
Techniques
Techniques

Chemicals Apparatus
Barium chloride, BaCl2 Bunsen burner
Copper (II) nitrate, Cu(NO3)2 Clamps, rings
Potassium nitrate, KNO3 Florence flask
Potassium permanganate, KMnO4 Test tubes
Sulfuric acid, H2SO4

OBJECTIVE
In this experiment the students will learn to use some of the basic laboratory techniques that
take advantage of the physical properties of substances. In the first part of this experiment, the
students will learn how to use a balance and perform a simple weighing. In the second part,
students will learn how to separate chemical substances by using decantation, crystallization
and distillation.

THEORY
Properties are characteristics of a substance that enable us to identify it and to distinguish it
from other substances. The properties of a matter can be categorized as physical or chemical.

Direct identification of some substances can readily be made by simply examining them. For
example, we see color, size, shape, and texture, and we can smell odor and recognize a variety
of tastes. Thus, copper can be distinguished from other metals on the basis of its color.

Physical properties are the properties that can be observed without altering the composition of
the substance. Whereas it is difficult to assign definitive values to such properties as taste,
color and odor, other physical properties, such as melting point, boiling point, solubility,
density, viscosity, and refractive index, can be expressed quantitatively.

For example, the melting point of copper is 1087 0C, and its density is 8.96 g/cm3. As
you probably realize, a specific combination of properties is unique to a given substance,
thus making it possible to identify most substance just by careful determination of several
properties.

14
Solubility is the amount of a substance that can be dissolved in a given quantity of solvent at a
given temperature. It depends on both the substance and the solvent. The solubility of
substances in one another varies widely. A factor that can limit solubility is the relative forces
of attraction between the species. As a general rule: “like dissolves like”. A polar substance is
defined as polar, if it has an unbalanced localized charges and has a dipole moment. When a
substance is polar, it will be dissolved in a polar solvent. Similarly if the substance is non-
polar, it will be dissolved in a non-polar solvent. Usually, substances have limited solubility in
one another. If the amount of substance present in a given solvent is greater than the solubility
value precipitation occurs.

A chemical property is a property of a substance that is observed when a substance undergoes

a chemical change. A chemical change is a type of change that also changes the identity of a
substance due to breakage and formation of new chemical bonds.

Chemical changes and the chemical properties of substances are directly linked to the physical
properties of a substance. Some common chemical properties are heat of combustion,
enthalpy of formation, toxicity, and flammability.

A mixture is the result of combining two or more substances that do not react chemically. In
order for a solution or combination to be labelled as a mixture, it must be possible to separate
the individual components through physical means, without using chemical reactions.

There are two types of mixture which are homogenous mixture and heterogeneous mixture.
Some mixtures do not have the same composition, properties, and appearance throughout.
Such mixtures are heterogeneous. Mixtures that are uniform throughout are homogeneous
such as air. Salt, sugar and many other substances dissolve in water to form homogeneous
mixtures that are also called solutions.

In this experiment, the methods you will use for the separation depend upon differences in
physical properties, and they include the following:

Part A: Decantation is simply pouring off the liquid over a precipitate in order to separate
the precipitate from the liquid (see Figure1.1). The formation of precipitate and
separation by decantation will be performed.

Part B: Separation of two water-soluble salts on the basis of their different solubility, at
room temperature, will be studied and recrystallization method will be performed
(see Figure1.2). In this part, remember that Cu(NO3)2 is blue and KNO3 is white.

Part C: Water will be separated from potassium permanganate solution by distillation (see
Figure1.3). Distillation is a physical process in which an easily-evaporized
(volatile) liquid is separated from another substance by evaporating and then
condensing. Thus, it is used to separate substances of different volatilities, different
boiling points.

When the potassium permanganate solution is heated, water vapor will be driven
off first; because the boiling point of potassium permanganate solution is much
higher than that of water.

15
PROCEDURE
A. Decantation (Precipitation of Barium Sulfate, BaSO4)

1. Take two test tubes. Fill one of them with barium chloride (BaCl2) solution, and the other
one with dilute sulfuric acid (H2SO4) solution.

2. Mix 5.0 mL of barium chloride (BaCl2) solution with 5.0 mL of dilute sulfuric acid
(H2SO4) solution as shown in Figure 1.1 and observe what happens. Write your
observations on the report sheet.

3. Allow the contents of the test tube to stand until all solid BaSO4 has settled down till the
end of laboratory period (Continue with part B.)

4. What is the color of the precipitate?

5. At the end of the laboratory period, you will be able to see the clear solution on the top
of the precipitate. Separation of a solid and liquid by pouring off the liquid is called
decantation. Pour off the liquid part into a test tube to separate the solid.

Transfer the separated liquid to the acid waste container and clean your
glassware.

Figure 1.1 Decantation method

16
B. Recrystallization

1. Take about 10.0 g of potassium nitrate, KNO3 – copper nitrate, Cu(NO3)2 mixture (It is
already a solid/solid mixture, you do no need to mix) in a 100 mL beaker and add 10.0
mL of water into the beaker.

2. Heat the beaker gently on a Bunsen burner until all of the solid has been dissolved. Cool
the beaker to room temperature by setting it aside on the bench at a safe place. Continue
with part C.

3. Once your solution is at room temperature, cool it further by passing tap water from
outside of the beaker until no more crystal formation is observed.

4. Fold your filter paper and configure a filtration set-up as shown in Figure 1.2

5. Filter your mixture using the filtration set up. Save the filtrate (solution that passes
through a filter paper). Wash the solid on the filter paper with 2-3 mL of cold water once
or twice.

6. Observe the color of the solid and the filtrate. From the color of the solution and the solid,
identify two compounds. Report your observation.

Discard the crystals and the solution into the waste container labeled as
“Cu(NO3)2 - KNO3 mixture” and clean your glassware.

Saturated
solution Filter paper

a b

Filtrate

c d
Fold a piece of filter paper in half (b). Fold the filter paper
in quarters (c). Open the filter paper into a conical shape (d)

Figure 1.2 Techniques to fold a filter paper (left) and a simple filtration set-up (right).

17
C. Separation by Distillation
1. First, a simple distillation set-up must be constructed as shown in the Figure 1.3.

Clamp
Flouresence
flask

Wire
gauze Test tube

Tripod
Universal
stand
Bunsen
burner

Figure 1.3 Distillation set-up

2. Transfer 20.0 mL potassium permanganate solution (solid KMnO4 dissolved in water) into
100 mL Florence flask.

3. Place the rubber stopper on to the Florescence flask carefully so that the vapor does not
escape from the flask.

4. Light the Bunsen burner and adjust it to have a small hot flame.

Your assistant will show how to use the Bunsen burner.

5. Heat the KMnO4 solution until 2-3 mL of liquid have been distilled into the test tube.

6. Observe the color of the distillate and interpret whether concentration of KMnO4 solution
in Florence flask increased or decreased. In your report sheet, write how you made that
decision. Write your observations and interpretations also to the report sheet.

Remaining KMnO4 solution should be disposed into the aqueous waste container.
Clean your glassware.

18
7. Continue with part A.5 and B.3.

19
 The Law
The Law of
of Definite
Definite
Proportions
Proportions

Chemicals Apparatus
Test tube
Manganese (IV) oxide, MnO2
Stirring rod
Potassium chlorate, KClO3
Bunsen burner
Potassium chloride, KCl
Metal spatula

OBJECTIVE
In this experiment the student will learn the law of definite proportions and the law of
conservation of mass and gain experience in gravimetric analysis (analysis by weighing) as
well as error calculations.

THEORY

Two laws of chemical change are the law of conservation of mass and the law of definite
proportions. According to the law of conservation of mass, there is no detectable change
in the mass during the course of a chemical reaction. The law of definite proportions states
that a pure compound always contains the same proportions of its constituent elements,
regardless of its origin or the way of preparation. Therefore, the composition of a given
compound has some definite value fixed by the atomic weight and the molecular formula.

The mass percent of an element X in a compound MaXb can be calculated by the following
equation:

b. (Atomic weight of X)
Mass % of X = x 100
Formula weight of Ma Xb

20
 Example 2.1

One mole of V2O5 contains 5 moles of O atoms, as it is clear from its formula.
Calculate the % O by weight in V2O5. (Atomic Wts: V= 50.9 g/mol;
O= 16.0g/mol).

Solution:

5 x (Atomic weight of O)
Mass % of O = x 100
Formula weight of V2 O5

5 x 16.0
Mass % of O = x 100 = 44.0 % by weight
(2 x 50.9) + (5 x 16.0)

Error and Percent Error:

Error is the difference between the value found experimentally and the correct (real or
theoretical) value; it may have a positive or negative value. Percent error can be calculated
by dividing the value of the error by the theoretical (correct) value and multiplying by 100.

Error = experimental value − theoretical value

exp. value − theo. value

% Error = x 100
theoretical value

Example 2.2

A compound contains 39.2 % oxygen by weight (theoretical value). In this

compound, Student A and student B found 36.3 % and 44.5 %, as experimental %
oxygen by weight, respectively. Calculate the error and % error in the result of
each student.

Solution:
Student A:

Error = 36.3 − 39.2 = −2.9

36.3 − 39.2
% Error (A) = x 100 = −7.4 %
39.2

21
 Student B:

Error = 44.5 − 39.2 = +5.3

44.5 − 39.2
% Error (B) = x 100 = 13.5 %
39.2

KClO3, decomposes when heated in the presence of a catalyst according to the following
reaction,
Δ
2KClO3 (s) → 3O2 (g) + 2KCl(s)

In this experiment, the percent oxygen by weight in KClO3 will be determined from the
weight difference between the constituents before and after heating. Since O2 is a gas and
leaves the contents as it is formed, the observed mass difference is due to the loss of
oxygen gas. In this experiment iron oxide, Fe2O3, or manganese dioxide, MnO2, can be
used as a catalyst to speed up the reaction. A catalyst is a substance that speeds up the
reactions without being consumed.

PROCEDURE

A. Percent Oxygen in Potassium Chlorate

Write all the mass measurements you have obtained during the experiment on your report
sheet. Calculations are shown in the report sheet.

1. In a clean and DRY test tube, place about one tea-spoonful of MnO2. If test tube is not
dry, heat the test tube directly on the flame of Bunsen burner. MnO2 catalyst does not
work properly on wet conditions.

2. Heat MnO2 in the test tube while holding the test tube diagonal as possible using a metal
tongs (see figure 2.1)

3. Heat until all the moisture is gone and dry also the moisture accumulated in the upper
part of the test tube.
4. Allow the test tube to cool down to the room temperature, and then weigh as W0 (total
mass of test tube and catalyst). It is not necessary to weigh empty test tube. Make sure
to have a stable reading up to two decimal points.
5. Take approximately 3 grams of KClO3 on weighing paper and add it into catalyst. Mix
KClO3 and catalyst by using stirring rod until you see the same color all over in the tube
and weigh the tube again as W1 (total mass of test tube, catalyst and KCIO3) .

22
 Figure 2.1 Heating test tube

6. Calculate the weight of KClO3 as W2.

7. Heat the mixture in the test tube, first gently from a distance then directly on fire about
15 minutes.

 The mixture will first melt, then effervesce (produce gas), and then solidify into a
puffy mass.

Be sure not to apply the flame too long to a single spot, or the glass may
crack.

8. Cool the test tube to room temperature by setting aside on the bench at safe place. Shut
off the burner. Allow the test tube cool completely and weigh it after cooling, record
the weighing as W3.
9. Heat the test tube and its contents for another 5 min, cool and reweigh as W4.
10. If the values of W3 and W4 are within ± 0.05 g, you may assume that all the oxygen
has gone.

If not, you must heat and reweigh until two consecutive weighings are similar. List
the weighing results on the report sheet. Your last weighing is Wf, obviously, Wf must
be the same as W4.

Discard your test tube directly to glass waste.

11. Calculate the mass of oxygen given off, report as Wox.
12. Calculate % oxygen by weight in KClO3. This is the experimental percentage.
13. Calculate the theoretical % of oxygen in KClO3. (At.wt (g/mol) O=16.0; Cl=35.5;
K=39.1)
14. Calculate % error.

23
 B. Analysis of an Unknown KClO3 - KCl Mixture Sample
The composition of an unknown KClO3 - KCl mixture will be determined by heating the
sample and measuring the weight loss.
1. Obtain an unknown sample (KCl-KClO3 mixture) from your assistant and write
unknown number to report sheet.

2. In a clean and DRY test tube, place about one tea-spoonful of MnO2. If test tube is not
dry, heat the test tube directly on the flame of Bunsen burner. MnO2 catalyst does not
work properly on wet conditions.

3. Heat MnO2 in the test tube while holding the test tube diagonal as possible using a metal
tongs.

4. Heat until all moisture is gone and dry also the moisture accumulated in the upper part of
the test tube.

5. Allow the test tube to cool down to the room temperature, and then weigh as W0/ (total
mass of test tube and catalyst). It is not necessary to weigh empty test tube. Make sure
to have a stable reading up to two decimal points.
6. Add unknown mixture into catalyst. Mix unknown mixture and catalyst by using stirring
rod until you see the same color all over in the tube and weigh the tube again as
W1/(total mass of test tube, catalyst and KCIO3-KCl).

Do not forget to write the number of unknown to the report sheet.

7. Calculate the weight of KClO3 as W2/.

8. Heat the mixture in the test tube, first gently from a distance then directly on fire about
15 minutes.

 The mixture will first melt, then effervesce (produce gas), and then solidify into a
puffy mass.

9. Cool the test tube to room temperature by setting aside on the bench at safe place. Shut
off the burner. Allow the test tube cool completely and weigh it after cooling, record the
weighing as W3.
10. Heat the test tube and its contents for another 5 min, cool and reweigh as W4 .

11. If the values of W3  and W4  are within ± 0.05 g, you may assume that all the oxygen has
gone thus W4 will be taken as Wf .

If values of W3 and W4 are not within ± 0.05 g, you must heat and reweigh until two
consecutive weightings are similar. List the weighing results on the report sheet. Your
last weighing is Wf.

Discard your test tube directly to glass waste

.
12. Calculate the mass of oxygen released, report as Wox/ .

24
13. Calculate % oxygen by weight in unknown. This is the experimental percentage (%
Oxygen in unknown: Value from Part B 12).

14. Calculate the percent KClO3 by weight in your unknown sample (% Oxygen in pure
KClO3 : Value from Part A 13).

25
 Enthalpy of Formation
Enthalpy of Formation

Chemicals Apparatus
Ammonia, NH3
Ammonium chloride, NH4Cl Insulated cup
Ammonium sulfate, (NH4)2SO4 Thermometer
Hydrochloric acid, HCl Beaker
Sulfuric acid, H2SO4

OBJECTIVE
In this experiment, the enthalpy of formation of various ammonium salts NH4X(s) (where X
can be Cl or SO4) will be determined by measuring the heat of neutralization (1) and the heat
of dissolution of NH4X (2) by using the known enthalpy of formation values of NH3(aq) and
HX(aq).

NH3 (aq) + HX(aq) → NH4 X(aq) ΔHneut (1)

NH4 X(s) + H2 O(l) → NH4 X(aq) ΔHdiss (2)

THEORY
The enthalpy of formation per mole of a compound is the ΔH accompanying in the
formation of one mole of the compound from its elements, in their standard states. Direct
measurement of enthalpies of formation is often difficult experimentally, so indirect
methods involving enthalpies of reaction are frequently used instead.

Hess’s Law states that the change in a thermodynamic property (such as enthalpy) depends
only on the initial and final states and is independent of the path followed. In other words,
adding several consecutive reactions gives a net reaction for which the ΔH is simply the sum
of the ΔH values for the component reactions.

26
 1 3
N2 (g) + 2 H2 (g) → NH3 (g) ΔH of form. of NH3 (g) = ΔH1 = -45.8 kJ
2

NH3 (g) → NH3 (aq) ΔH of dissolution = ΔH2 = -35.4 kJ

1 3
N2 (g) + 2 H2 (g) → NH3 (aq) ΔH of form. of NH3 (aq) = ΔH1+ ΔH2 = -81.2 k
2

Enthalpies of reaction follow simple rules:

1- The enthalpy of reaction is proportional to the amount of reactant that reacts.
2- Reversing a reaction change the sign of ΔH
3- The enthalpy of reaction depends on the physical state of the reactants and products.

Example 4.1

Calculate ΔH for the reaction

2C(s)+H2 (g)→𝐶2 H2 (g)

Given the following chemical equations and their respective enthalpy

changes:
5
C2H2(g)+ 2 O2 (g)→2C𝑂2 (g) + 𝐻2 𝑂(𝑙) ΔH= -1299.6 kj
C(s)+O2 (g)→C𝑂2 (g) ΔH= -393.5 kj
1
𝐻2 (g)+ 2 O2 (g)→𝐻2 𝑂(l) ΔH= -285.8 kj

Solution
The target equation has C2H2 as a product, we turn the first equation
around; the sign of ΔH is therefore change.

The desired equation has 2C(S) as a reactant, so we multiply the second

equation and its ΔH by 2.

5
2CO2(g)+H2 𝑂(l)→𝐶2 𝐻2 (g) + 2 𝑂2 (𝑔) ΔH = +1299.6 kj
2C(s)+2O2 (g)→2C𝑂2 (g) ΔH = -787 kj
1
𝐻2 (g)+ 2 O2 (g)→𝐻2 𝑂(l) ΔH = -285.8 kj

2C(s)+H2 (g)→𝐶2 H2 (g) ΔH = 226.8 kj

27
 Figure 4.1 Experimental set-up for enthalpy of formation

The way in which the ΔH of your reactions will be determined is to measure temperature
changes of the system. The experimental setup consists of an insulated cup, a thermometer
and a water solution of reactants or products. (Figure 4.1) To simplify matters the system
will be limited only to the water solution of reactants or products. The experiment is
designed to make it possible to correct any heat exchanges between the surroundings (cup,
thermometer and air) and the system (water plus reactants or products). This will allow us to
define the system as adiabatic (q = 0; no heat exchange between system and surroundings).

In addition to this, the difference between heat and temperature should be known.

Heat is the total amount of energy (both kinetic and potential) possessed by the molecules in
a piece of matter and measured in Joules.

Temperature is not energy like heat and it relates to the average (kinetic) energy of
microscopic motions of a single particle in the system per degree of freedom. It is measured
in Kelvin (K), Celsius (C) or Fahrenheit (F).

qsystem = 0 = n ΔHreaction,m + Cp ΔH
The subscript p refers to constant
pressure
n ΔHreaction = - Cp ΔT

where, ΔHreaction is the enthalpy of reaction for 1 mole reactant. If heat is generated
(exothermic, ΔHreaction< 0) by the reaction this heat must be absorbed entirely within the
system itself as the system being adiabatic cannot exchange heat with the surroundings. The
resulting increase in the temperature, ΔT of the system will depend inversely on the heat
capacity, Cp, (heat required to increase the temperature of the system by 1.0 °C) of the entire
system at constant pressure. The larger the Cp, the smaller the ΔT will be necessary to
absorb the heat from the reaction:

28
 Likewise, if the reaction is endothermic (ΔHreaction  0) heat taken for the reaction must
come from the energy of the system itself, resulting in a decrease in the temperature of
the system.

NOTE: For water;

Cp per gram for the system is equal to Cp per gram for water, which is
4.184 J/(g.°C)
The density of the solution= d(H2 O) = 1.00 g/mL, mass of the solution, m(solution);

m(solution)  𝐦(𝐇𝟐 𝐎) = 𝐝(𝐇𝟐 𝐎) V(solution) = 1.00 (g/mL) V(mL) = V(g)

n ΔHreaction = 𝚫𝐓(°𝐂) 𝐦(𝐇𝟐 𝐎) 𝐂𝐩 (𝐇𝟐 𝐎) J/(g °C)

n ΔHreaction = - ΔT(°C) V(g) 4.184 (J/g.°C) (do not forget the minus sign)

In order to measure ΔT, a series of temperature vs. time measurements should be made and
plotted. From the rate of temperature change before and after reaction occurs, it is possible
to correct for any heat exchange between the system and surroundings. Extrapolation to the
time of mixing, as shown in the following Figure 4.2 (for an exothermic reaction), will
give ΔT.

ΔT

Figure 4.2 Temperature vs. time plot for an exothermic reaction.

29
Sample Calculation for Determining the Volume of HCl and mass of NH4Cl

1. Calculate volume of 1.5 M HCl solutions required in Part A in the

procedure.

𝑁𝐻3(𝑎𝑞) +𝐻𝐶𝑙(𝑎𝑞) →𝑁𝐻4 𝐶𝑙(𝑎𝑞)

MB VB = MAVA
1.5M x 50ml = 1.5M x VA
VHCl = 50 ml

2. Calculate the mass of NH4Cl required in Part B of the procedure. (N = 14.0

g/mole, H = 1.01 g/mole, Cl = 35.5 g/mole)
𝑛
M=
𝑉

n = 1.5M x 50mL = 0.075 mol

m = Mw x n = 53.54 g/mol x0.075 mol = 4.02g

The reactions and equations for the calculation of ΔHf° of NH4Cl.

𝑁𝐻3(𝑎𝑞) +𝐻𝐶𝑙(𝑎𝑞) →𝑁𝐻4 𝐶𝑙(𝑎𝑞) ΔHneut

-1/𝑁𝐻4 𝐶𝑙(𝑠) →𝑁𝐻4 𝐶𝑙(𝑎𝑞) -1/ΔHdiss
𝑁𝐻3(𝑎𝑞) +𝐻𝐶𝑙(𝑎𝑞) →𝑁𝐻4 𝐶𝑙(𝑠)

ΔHrxn = ΔHNeut + (-ΔHdiss)

ΔHrxn =ΔH 𝑓0𝑁𝐻4 𝐶𝑙 – (n Δ𝐻𝑓 𝑁𝐻3 + Δ𝐻𝑓 𝐻𝐶𝑙)

30
 PROCEDURE

A. Neutralization
1. Get a Styrofoam cup from the lab technician. Place 50.0 mL of 1.5 M NH3 solution into
a clean beaker and place the beaker into the Styrofoam cup.
2. Take 50.0 mL of 1.5 M HCl solution to another beaker.
3. Place a thermometer inside the NH3 solution and close the lid. Start recording the
temperature at every 30 seconds intervals for 3 minutes. You should record the
temperature as an integer number or at intervals of 0.5 °C.
4. Immediately after the last reading open the lid, add the HCl solution all at once onto
NH3 solution in the Styrofoam cup and close the lid.

5. Swirl the Styrofoam cup gently for 10 seconds.

6. Continue recording temperature every 30 seconds for 5 minutes while swirling the
solution occasionally.

7. Repeat steps 1-5 with 25.0 mL of 1.5 M H2SO4 (instead of 1.5M HCl solution).

Dispose your chemicals into aqueous waste container!

B. Dissolution
1. Weigh approximately 4.0 g of NH4Cl on a weighing paper and record the exact amount
on your notebook.

2. Place 100.0 mL of tap water into a clean beaker and place the beaker into the
Styrofoam cup.

3. Place a thermometer into the water and close the lid. Start recording the temperature at
every 30 seconds for 3 minutes. You should record the temperature as an integer
number or at intervals of 0.5 °C.

4. Immediately, add the weighed amount of NH4Cl, and close the lid. Start recording the
temperature at every 30- seconds intervals for 5 minutes.

5. Repeat the procedure with approximately 5.0 g of (NH4)2SO4 with 75.00 mL of tap
water instead of NH4Cl.

Dispose your chemicals into aqueous waste container!

DATA ANALYSIS

1. Plot temperature (T, °C) versus time (t, sec) graphs for each measurement using your
data and estimate ΔHneut for HCl(aq) and H2SO4(aq) and ΔHdiss for NH4Cl(s) and
(NH4)2SO4(s).

31
2. Using the data given in the following table, calculate the ΔHformation of NH4Cl(s), and
(NH4)2SO4(s).

Compound ΔHf ° (kJ/mol)

NH3(aq) – 81.2
HCl(aq) – 165.1
H2SO4(aq) – 884.2

32
 Solutions

Chemicals Apparatus
Alcohol
Copper (II) Sulfate, CuSO4 Glass rod
Oil Graduated cylinder (10 mL)
Paraffin in solid phase Metal spatula
Potassium nitrate, KNO3 Test tubes
Sodium acetate, NaC2H3O2.3H2O Thermometer
Sodium hydroxide, NaOH
Sugar
Tap water

OBJECTIVE
In this experiment, the students will learn about the factors that affect solubility and the
rate of dissolution.

THEORY
A mixture forms when two or more substances, that do not react chemically, are combined
such that each substance retains its own chemical identity. The individual components in a
mixture can easily be separated by physical means such as decanting, filtration, distillation
etc.

There are two types of mixtures: homogenous mixtures and heterogeneous mixtures.
Heterogeneous mixtures such as granite do not have the same composition, properties, and
appearance throughout. On the other hand, homogenous mixtures are uniform throughout.
Salt, sugar and many other substances dissolve in water to form homogeneous mixtures.
Homogenous mixtures are also called solutions. In a solution, the substance present in the
greatest quantity is called the solvent and the other substances are called solutes.

The solutes and the solvent that make up a solution can be solids, liquids, or gases. For the
components of different types of solutions are listed in Table 7.1.

33
 Table 7.1 Types of solutions

Solute Solvent Solution Examples

Air (O2, Ar, CO2 in N2), natural gas (C2H6 C3H8 in
Gas Gas Gas
CH4)
Gas Liquid Liquid CO2 in H2O
Vinegar (CH3COOH in H2O), vodka (C2H5OH in
Liquid Liquid Liquid
H2O)
Solid Liquid Liquid Saline solution (NaCl in H2O)
Gas Solid Solid H2 in Pd
Solid Solid Solid Brass, alloy of Cu and Zn

A solution forms when the attractive forces between the solute and the solvent particles are
comparable or greater than those that exist in between solute particles or between the
solvent particles. For instance, a polar (or ionic) solute such as NaCl is soluble in water, a
polar solvent.

Substances that mix in all proportions, forming solutions, are said to be miscible; those that
do not dissolve significantly in one another are said to be immiscible.

Water is considered as the universal solvent since it is capable of dissolving a variety of

different substances. As mentioned above, the solubility of a substance in water depends
on the relative magnitudes of intermolecular forces solute-solute and solvent-solvent
compared to solute-solvent interactions. In addition, the solubility of a substance in water
depends on the natural tendency of the systems to become more disordered. The heat of
solution (enthalpy of solution) is the difference enthalpy change associated with the
dissolution of a substance in a solvent at constant pressure. In other words, it is the
difference in the energy required for the separation of solute-solute and solvent-solvent
particles and the energy released due to solute-solvent interaction. The overall enthalpy
change upon solution formation may be either positive or negative. If the solute-solvent
interactions are stronger than those of the solute-solute and solvent-solvent interactions,
then the solution process is exothermic and solubility decreases as the temperature
increases. If the solute-solvent interactions are weaker than those of the solute-solute and
solvent-solvent interactions, the solution process is endothermic and solubility increases as
the temperature increases.

34
PROCEDURE
A. Nature of Solute and Solvent

1. Take 6 test tubes and to test the solubility of sugar, sodium chloride and paraffin in each
of the following solvents: water and alcohol (ethanol) at room temperature.

2. Put 2 to 3 mL of the solvent (water or alcohol) and a lump of a solute (not more than half
of size of a pea, sugar or sodium chloride or paraffin) in a test tube. Swirl your test tube
gently. Record your observations in the report sheet. Make sure to identify each substance
as soluble (s), slightly soluble (ss), or insoluble (i) in both of the solvents.

Note
20-25 drops equals to ~ 1 mL, adjust the volume approximately by counting the drops
of solvent for one tube, then mark the level of solvent on the other tubes.

Dispose your alcohol-water waste into the aqueous waste container.

Discuss your observations (the solubility of each solute in both of the solvents) by
considering the chemical structures and the polarities of each solute-solvent pair.

3. Take a clean test tube, and fill it with 1 mL of water. Add 2 mL of alcohol dropwise (one
drop at a time) on top of the water in the test tube. Record your observations about the
miscibility (m), or immiscibility (im) of alcohol and water in your report sheet.

4. Take another clean test tube, and fill it with 1 mL of alcohol. Add 2 mL of water dropwise
on top of the alcohol in the test tube. Record your observations about the miscibility (m),
or immiscibility (im) of alcohol and water in your report sheet.

5. Repeat A3 and A4 using A) oil-water and B) oil-alcohol. Record your observations about
the miscibility (m), or immiscibility (im) of oil and water in your report sheet.

Dispose your alcohol-water waste into the aqueous waste container and oil-water
and oil-alcohol waste into the oil waste container.

Wash the test tubes carefully with detergent using a brush.

Think about your observations in A3 and A4. Is there a difference in the

miscibility/immiscibility of the liquids when the order of mixing is changed?

Think about your observations in A5-A and A5-B. Is there a difference in the
miscibility/immiscibility of the liquids when the order of mixing is changed?
Compare your results for A3, A5-A and A5-B. State in which case you did observe the
formation of two separate layers. Identify also the liquids as the top and the bottom layer.

35
 B. Effect of Particle Size

1. Take two clean test tubes. Place approximately 1 spatula of CuSO4 powder in in one
of the test tubes, and a small piece (about pea size) of CuSO4 crystal into the other test
tube.
2. Add approximately 2 mL of water to each of the test tubes and swirl the test tubes
gently.

3. Record your observations regarding the dissolution rates of the powder and crystal
forms of CuSO4 in water. Make sure to compare and contrast the rate of dissolutions.

Dispose your waste into the aqueous waste container.

C. Effect of Temperature on Solubility

1. Carefully measure 5 mL of water into a clean test tube, using a pipette.

2. Weigh approximately 4g of potassium nitrate, KNO3 on a weighing paper and transfer
it into the test tube with water.
3. Heat the test tube gently (do not boil) using a Bunsen burner until the solid completely
dissolves.
4. Turn of the Bunsen burner and insert a thermometer into the test tube. Set the test tube
aside and allow it to cool down. During that time, carefully observe the test tube until
you see the formation of the crystals. Record the temperature at which you started
observe the crystal formation.
5. Weigh additional 2 grams of KNO3 and transfer it also into your test tube (the test tube
you used in C1-C4). Repeat C3 and C4. Make sure to record the temperature at which
you started to observe the crystal formation.

6. Repeat C5 with additional 2 grams of KNO3.

Dispose your waste into the aqueous waste container.

In your report sheet, plot the solubility (g/ 5 mL) of KNO3 in water versus the
temperature graph.

D. Heat of Solution
1. Place 5 mL of water in a small test tube. Insert a thermometer and determine the
temperature of the water.

Do not hold the test tube in the palm of your hand, as this may affect the
temperature.
2. Remove the thermometer and add one full spatula of NaCH3COO.3H2O into the water
in the test tube.

36
3. Swirl the test tube gently until all the solute dissolves. Insert the thermometer quickly
back into the rest tube and record the the temperature of dissolution.
4. Repeat D1-D3 using NaOH, instead of NaCH3COO.3H2O.

Dispose your waste into the aqueous waste container.

Based on your observation, describe how the temperature of the water changed based on
the identity of the added salt, NaCH3COO.3H2O vs NaOH. Classify each reaction as
endothermic or exothermic.

37
 Colligative Properties
Colligative Properties

Chemicals Apparatus
Distilled water Beaker (250 mL)
Ethylene glycol Bunsen burner
Sodium chloride (NaCl) crystals Crushed ice
1.0 m sodium chloride (NaCl) solution Glass rod
1.0 m sucrose (sugar, C12H22O11) Styrofoam cup
solution Test tube
Unknown molecular solid Thermometer

OBJECTIVE
In this experiment the students will become familiar with two of the colligative properties,
freezing-point depression and boiling-point elevation. In addition, they will learn how to
determine the molar mass of an unknown substance using colligative properties.

THEORY

Colligative Properties

Colligative properties of solutions are physical properties that depend on the quantity (e.g.
concentration) but not on the nature (kind or identity) of the solute particles. Colligative
properties include vapor-pressure lowering, boiling-point elevation, freezing-point
depression and osmotic pressure.

In this experiment, two of the colligative properties, freezing-point depression and boiling-
point elevation, will be examined.

38
a- Freezing Point Depression
T
The freezing point of a liquid is defined
as the temperature at which the first l
crystals of the pure solvent form in l s
equilibrium with the liquid at normal
atmospheric pressure. Freezing point of s
a liquid can easily be determined
through the construction of a cooling
curve such as the one given in Figure
8.1. t2
t0 t1 time
Figure 8.1. Cooling curve of a liquid

A cooling curve for a liquid shows the variation in temperature (T) with time (t) as the
liquid is cooled down in a constant-temperature bath. In an experiment like this, first the
temperature of the liquid will decrease in time (to) until the liquid starts to get converted to
the solid form. The temperature at which the liquid converts to the solid form can be
assigned as the freezing point. The temperature of the solution will remain constant during
the liquid-solid conversion (t1).

During freezing, the particles line up in a defined geometric pattern and lose their velocity
as they go from the liquid state to the solid state. During that transition both the kinetic
and the potential energy of the particles decrease and the energy is released to the outside.
The energy released compensates for the heat removed by cooling and as a result the
temperature stays constant during freezing.

Once the conversion of the liquid to the solid is complete the temperature will continue to
decrease with time.

The freezing point (Tf) of a solution is always lower than that of the pure solvent. The
decrease of the freezing point of a pure solvent on addition of a non-volatile solute is called
the freezing-point depression. The freezing-point depression can be calculated as;

Tf = Tf (solution) – Tf (solvent)

Note that because the solution freezes at a lower temperature than does the pure solvent,
the value of Tf is negative

The freezing-point depression has many practical applications in our daily life;

 The antifreeze used in a car’s cooling system is a solution of ethylene glycol in water,
and has a lower freezing point than pure water. The freezing point of a 60-70% ethylene
glycol solution can go down to -37oC, where the freezing point of pure water is 0oC. If
pure water is used in a car’s cooling system in a cold winter day, below 0oC the expansion
of the water due to freezing might seriously damage the engine of the car.

 Windshield washing fluids contain mostly methanol to lower the freezing point of the
solution in addition to the cleaning agents.

39
 The icy roads will be salted in cold winter days. The salt dissolves into the liquid water
in the ice, lowers its freezing point and therefore melt the ice.
The freezing-point depression, Tf of a solvent in a dilute solution can also be calculated
using the formula below where i is the van’t Hoff factor, Kf is the molal freezing-point
depression constant (°C/m) and m is the total molality of the solution (m). The van't Hoff
factor is the ratio between the actual concentration of particles produced when the
substance is dissolved and the concentration of a substance as calculated from its mass. For
most non-electrolytes dissolved in water, i is essentially 1. For most ionic compounds
dissolved in water, i is equal to the number of discrete ions in a formula unit of the
substance. In another words, for ionic solutions i is the total concentrations of ions rather
than the concentration of ionic substance is important. i can be determined by noting the
number of ions per formula unit. In reality, the experimentally determined i value is less
than that is predicted from the formula (except for very dilute solutions) as ions in solution
can form ion-pairs. Kf is a constant that is specific for each solvent.

Tf = - i. Kf . m

Some typical values of Kf along with the freezing points of the pure solvents are given
in Table 8.1.

Normal freezing Normal boiling

Solvent point (0C) Kf (oC/m) point (0C) Kb (oC/m)

Benzene (C6H6) 5.5 5.12 80.1 2.53

Chloroform (CHCl3) - 63.5 4.68 61.2 3.63
Ethanol (C2H5OH) -114.6 1.99 78.4 1.22

Table 8.1 Molal Freezing-Point Depression and Boiling-Point Elevation Constants

Molality, m, is defined as the number of moles of a solute in 1000 g of the solvent.

wt of solute(g)
⁄ g
Molar mass of solute( )
Number of moles of solute mol
Molality = =
kg of solvent wt of solvent(kg)

The molar mass of a solute can be determined by combining the equations given above,
basically by dissolving a known mass of a solute in a known mass of the solvent and
measuring the freezing point depression.

40
Example 8.1

Calculate ∆Tf if 0.10 mol ethanol is dissolved in 1.0 kg of water. Kf of water is

1.86 °C/m.

Solution
Tf = - Kf . m and m = n solute / kg solvent

0.10 mol
m= = 0.1 m
1.0 kg

Tf = –1.86 x 0.1 = – 0.19°C

Example 8.2

Calculate ∆Tf if 1.17 g of NaCl is dissolved in 2.0 kg of water.

Solution
As NaCl (Mwt (NaCl)= 58.5 g/mol) is an ionic substance it dissociates in water

H2 O
NaCl(s) → Na+(aq) + Cl−
(aq)

Tf = – i .Kf . m where i = 2 for NaCl

1.17 g
⁄58.5 g/mol
m(NaCl) = = 0.01 m
2.0 kg

Tf = – 2 x 1.86 x 0.01 = – 0.019°C

41
 Example 8.3

When 1.15 g of naphthalene is dissolved in 0.100 kg of benzene, the resulting

solution has a freezing point of 4.95 °C. What is the molecular weight of
naphthalene? Freezing point of benzene is 5.40 °C. Kf (benzene) = 5.120C/m.

Solution
∆T = 4.95 – 5.40 = – 0.45 °C

∆Tf − 0.45 ℃
m= = = 0.088 m
−K f − 5.12 ℃/mol

wt of solute(g)
⁄ g
MWt of solute( )
mol
wt of solute (g)
Molality = ⇒ MWt = wt of solvent (kg)x m
wt of solvent(kg) which yields

1.15 g
MWt = = 𝟏𝟐𝟖. 𝟎 𝐠/𝐦𝐨𝐥
0.100 kg x 0.088 mol/kg

b- Boiling Point Elevation

The boiling point of a liquid is defined as the temperature at which its vapor pressure
equals the external pressure, acting on the liquid surface. And the normal boiling point of
a liquid is the temperature at which its vapor pressure is equal to 1 atm (706 torr).

g
Tb l g

t1 t2 time

Figure 8.2. Heating curve of a liquid

In a heating curve for a liquid, which shows the variation in temperature (T) with time (t)
as the liquid is heated up in a constant-temperature, the boiling can be assigned as the
temperature at which the phase transition from liquid to gas occurs. In Figure 8.2, liquid
begins to be converted to gas at time t1 and the temperature remains constant until the
conversion is complete, from t1 to t2.

42
The boiling point (Tb) of a solution is always higher than that of the pure solvent. The
increase of the boiling point of a pure solvent on addition of a non-volatile solute is called
the boiling-point elevation. The boiling-point elevation can be calculated as;

Tb = Tb(solution) – Tb (solvent)

For dilute solutions, the boiling point elevation of a solvent is also directly proportional to
the total molality of the solution.

Tb = i . Kb . m

where T is the change in boiling point, boiling point elevation, °C

Kb is the molal boiling point elevation constant of the solvent, °C/m
m is the total molality of the solution, m
i is the van’t Hoff constant.

Some typical values of Kb along with the boiling points of the pure solvents are given in
Table 8.1.

PROCEDURE

A. Freezing Point Depression

1. Fill a 250 mL beaker with crushed ice up to two-third (2/3) level. Then add 20 g of NaCl
crystals and stir the content with a glass rod.

20 g NaCl

crushed ice mix well

Figure 8.3 Preparation of NaCl-ice mixture

43
2. Insert the beaker into a large Styrofoam cup and measure
the temperature of the ice/salt mixture. Make sure to
wait until the temperature reading is steady, -10°C or
lower.

3. Take 4 test tubes and label them as 1, 2, 3 and 4.

Figure 8.4 Set-up for A-2

4. Fill the test tube labeled as number 1 with tap water until it is about one-third (1/3)
full. Place the test tube in the ice/salt mixture which is already been placed in the
Styrofoam cup, and place the thermometer inside the test tube. Stir constantly, and
periodically lift the test tube just enough to observe the formation of crystals.

1/3

Figure 8.5 Set-up for A-4

5. Record the temperature at which you started to observe the formation of the ice crystals
in Table 1 in your report sheet.

6. Fill the test tube labeled as number 2 with 1.00 m sucrose solution until it is about
one-third full, and repeat step A4 and A5.

NOTE: 1.00 m sucrose solution is already prepared and can be taken directly from the
bottle.

7. Fill the test tube labeled as number 3 with 2.00 m sodium chloride (NaCl) until it is
about one-third full, and repeat A4 and A5.

NOTE: 2.00 m NaCl solution is already prepared and can be taken directly from the
bottle.

8. You need to prepare your own unknown solution according to the procedure given
below:
 Weigh an empty 100 mL beaker, and record the mass in your report sheet.

44
  Add 25 mL water into the beaker, weigh it again and record the mass in your report
sheet.
 Then add approximately 4.5 g of the unknown liquid into the beaker, weigh it again
and record the mass in your report sheet.
 Stir the solution thoroughly using a glass rod until you obtain a homogenous
solution.

Make sure the temperature of the ice/salt mixture is still

approximately –10 °C. Add more ice if necessary.

9. Fill the test tube labeled as number 4 with your unknown solution until it is about one-
third full, and repeat A4 and A5.

10. Obtain the molecular formula of the unkown liquid from your assistant. You will use
the molecular formula when calculating your % error.

Dispose your waste into aqueous waste container.

B. Boiling Point Elevation

1. Fill a 100 mL beaker with 50 mL of water, and add a few boiling chips in it to prevent
localized heating.

2. Place the beaker on a tripod as shown in Figure 8.6, carefully insert a thermometer
inside the beaker and start heating the solution using a Bunsen burner. Record the
temperature at which you started to observe the boiling of the water in Table 2 in
your report sheet.

3. Add 6 g of ethylene glycol into the water, stir thoroughly and record the boiling
temperature of the solution in Table 2 in your report sheet (density of ethylene glycol:
1.113 g/cm3 ).

4. Add another 6 g of ethylene glycol into the solution, stir thoroughly and record the
boiling temperature of the solution in Table 2 in your report sheet.

Calculate the molality of ethylene glycol solutions and Kb of water based on your data,
report them in Table 2.

45
 thermometer

clamp and stand

100 mL beaker

50 mL water

gauze and tripod

bunsen burner

Figure 8.6 Set-up for boiling point elevation

5. Repeat steps A1 toA4 using NaCl instead of ethylene glycol and report your results in
Table 3.

NOTE: Use the solid NaCl.

Dispose your waste into aqueous waste container.

CALCULATIONS

A. Freezing Point Depression

A.1. Calculate the freezing-point depression, ∆Tf, for sucrose solution

A.2.Using the calculated freezing-point depression (∆Tf, in °C) for the sucrose
solution, calculate Kf value for water using the equation Tf = i .Kf . m . Note
that the molality of the sucrose solution is 1.00 m and the sucrose is a non-
electrolyte, with the i value of 1 (i=1).

A.3.Calculate the freezing-point depression, ∆Tf, for NaCl solution. Using the
calculated freezing-point depression (∆Tf, in °C) for the NaCl solution and the
calculated Kf value for water in Calculations A.2, calculate the i value for NaCl.
Note that NaCl is an ionic solid and its molality is 2.00 m.
A.4. Assume that the unknown solute you used in part A8 was a non-electrolyte, with
an i value of 1. Calculate the freezing-point depression, ∆Tf, for the unknown
solution you prepared. Using the calculated freezing-point depression (∆Tf, in
°C) for the unknown solution and the calculated Kf value for water in
Calculations A.2, calculate the molality of the unknown solution.
A.5. Calculate the molar weight of the unknown solute, using the mass of the
unknown liquid and the mass of the water used during the preparation of the
solution.

46
A.6. Calculate the theoretical molecular mass of the unknown solute and the %
error in the experiment using the molecular formula that you obtained from
your assistant for the unknown liquid.

B. Boiling Point Elevation

B.1. Calculate the boiling-point elevation, ∆Tb, for ethylene glycol solutions.

B.2. Calculate the molal boiling-point elevation constant, Kb, of water, using both
of the ∆Tb values you obtained for the ethylene glycol solutions.
B.3. Calculate the average Kb value of water (experimental) and your % error in the
experiment using the theoretical Kb value for water (Theoretical Kb(H2O) =
0.52 °C/m).
B.4. Calculate van’t Hoff factor i for both of the NaCl solutions. Use theoretical Kb
value in your calculations.
B.5. Compare your results with the theoretical i value based on the formula unit of
NaCl. Calculate the average value of i for NaCl (experimental) and your %
error in the experiment.

B.6. Compare and contrast the effect of non-electrolyte solutes such as ethylene
glycol vs ionic solids such as NaCl on the boiling-point elevation of a solvent
such as water.

47
 Electrochemistry --
Electrochemistry
Voltaic Cells
Voltaic Cells

Chemicals Apparatus
Beaker
Cu strip
Multimeter
CuSO4 solutions
Salt bridge
Zn strip
Test tubes
ZnSO4 solutions
Pipette

OBJECTIVE
In this experiment the students will learn how to construct a voltaic cell to convert
chemical energy into electrical energy. The students will also learn how to measure the cell
voltage of the voltaic cell prepared using solutions with different concentrations.
Moreover, they will learn how to construct a concentration cell.

THEORY
Electrochemistry is the area of chemistry that deals with the relations between chemical
changes and electrical energy. Chemical reactions involving the transfer of electrons from
one reactant to another are called oxidation-reduction reactions or redox reactions. In a
redox reaction, two half-reactions occur; one reactant gives up electrons (undergoes
oxidation) and another reactant gains electrons (undergoes reduction).

A voltaic (galvanic) cell is a device that produces an electric current as the result of a
spontaneous electron transfer reaction. However, in an electrolytic cell, a non-spontaneous
reaction is forced to occur by application of an external voltage.

In order to generate electricity from the electron transfer during a redox reaction and to
covert chemical energy into electrical energy, the redox reactions has to be separated into
two different compartments. In such a redox reaction, oxidation reaction occurs at the
anode and the reduction reaction occurs at the cathode. Electrons flow spontaneously from
the negative anode to the positive cathode due to the potential differences between the
anode and cathode side. Here, the electrons flow from higher potential energy to lower
potential energy side spontaneously. The electrical circuit is completed by the movement
of ions through a salt bridge or a membrane. A salt bridge contains an electrolyte solution

48
whose ions will not react with other ions in the cell or with the electrode material but
counter balance the solutions are the redox reactions take place.

Electrons that are generated at the anode of an electrochemical cell are driven toward the
cathode by a thermodynamic tendency called the electromotive force (emf), measured in
volts. The emf is also called the cell potential and depends on both the identities of the
substances involved in the redox reactions as well as their concentrations. Under standard
conditions (25 0C, 1 atm, and 1.0 M for both the anode and cathode solutions) the cell
potential is equal to

° ° °
𝐄𝐜𝐞𝐥𝐥 = 𝐄𝐨𝐱𝐢𝐝𝐚𝐭𝐢𝐨𝐧 + 𝐄𝐫𝐞𝐝𝐮𝐜𝐭𝐢𝐨𝐧

Oxidation (anode) : Zn(s) → Zn2+ (aq) + 2e− Eoxº = 0.76 V

Reduction (cathode) : Cu2+ (aq) + 2e− → Cu(s) Eredº = 0.34 V
Overall reaction : Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s) Eºcell = 1.10 V

The maximum amount of work, wmax that can be obtained from a galvanic cell is equal to
the change in Gibbs free energy, G, for the process;

𝐰𝐦𝐚𝐱 = 𝚫𝐆 = −𝐧. 𝐅. 𝐄𝐜𝐞𝐥𝐥

where

 n is the number of electrons transferred

 F is Faraday’s constant, 1F = 96500 C

The change in Gibbs free energy can be used to derive a relation between the cell potential,
the concentration of the reactants and products, and the temperature.

𝚫𝐆 = 𝚫𝐆° + 𝐑𝐓 𝐥𝐧 𝐐

where

 Q is the reaction quotient (Q= anode/cathode)

 R is the gas constant, R= 8.314 Jmol-1K-1
 T is room temperature, T=298 K

Substituting 𝜟𝑮 = −𝒏. 𝑭. 𝑬𝒄𝒆𝒍𝒍 in the above equation, the Nernst equation is obtained. The
Nernst equation is useful in calculation of cell potential or concentration of the anode
and/or cathode solutions under non-standard conditions.

° 𝟎. 𝟎𝟓𝟗𝟐
𝐄𝐜𝐞𝐥𝐥 = 𝐄𝐜𝐞𝐥𝐥 − 𝐥𝐨𝐠 𝐐
𝐧

49
A voltmeter is inserted in the circuit to measure the cell voltage. The value of the voltage
or the electromotive force (emf), can be regarded as a quantitative measure of the tendency
for electrons to flow in the cell, in other words the tendency for the electrons to be
transferred from one reactant to the other.

Example 12.1

Calculate the cell potential for the following cell,

Zn l Zn2+ (0.75M) ll Cu2+ (0.20M) l Cu

Given the following:
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s) Eºcell = 1.10 V

Solution

° 0.0592
Ecell = Ecell − log Q
n
0.0592 0.75
= 1.10V − log
2 0.20

= 1.10 - 0.017

= 1.083 V

In this experiment, a Cu / Zn voltaic cell with the following net cell reaction will be used to
generate electrical energy. The overall reaction can be divided into two half-cell reactions,
an oxidation and a reduction halves, each one having a different electrode (by convention,
the electrode potentials are always given for reduction reactions). The species with half-
cell reactions that have more positive value of the reduction potentials have greater
tendency to be reduced.

Figure 12.1 Schematic representation of the voltaic cell to be constructed

50
The cell consists of the following parts:

1. A Zn strip (gray) immersed in ZnSO4 solution (colorless)

2. A Cu strip immersed in CuSO4 solution (blue)
3. A salt bridge constructed from a U-tube filled with concentrated and solidified
K2SO4.
4. A pair of wire with crocodile ends and banana plugs at each end in order to attach
metal strips to voltmeter terminals.

Concentration Cells

Since cell potential depends not only on the half-reactions occurring in the cell, but also on
the concentrations of the reactants and products in those half reactions, it is possible to
construct a voltaic cell in which both half reactions are the same, but there is a difference
in their concentration, which drives the current flow due to the chemical potential
differences.

In a concentration cell, electrons spontaneously flow from the half-cell with the lower
concentration (anode) to the half-cell with the higher concentration (cathode) until the
concentrations becomes the same in the both half cell.

Consider the electrochemical cell in which zinc metal is oxidized at the anode and zinc
ions are reduced at the cathode. Since the half-reactions are identical, the standard cell
potential, Eºcell, is zero.

Oxidation (Anode) : Zn(s) → Zn2+ (aq) + 2e− Eº = 0.76 V

Reduction (Cathode) : Zn2+ (aq) + 2e− → Zn(s) Eº = - 0.76 V

Overall reaction : Zn(s) + Zn2+ (aq)(cathode) → Zn2+ (aq)(anode) + Zn(s)

° ° °
Ecell = Eoxidation + Ereduction = 0.00 V

Because of the different concentrations in the two half-cells, the cell potential, Ecell, is
calculated using the Nernst equation:

° 𝟎. 𝟎𝟓𝟗𝟐 [𝐙𝐧𝟐+ ]𝐚𝐧𝐨𝐝𝐞

𝐄𝐜𝐞𝐥𝐥 = 𝐄𝐜𝐞𝐥𝐥 − 𝐥𝐨𝐠
𝐧 [𝐙𝐧𝟐+ ]𝐜𝐚𝐭𝐡𝐨𝐝𝐞

The formation of Zn2+ ions in the dilute half-cell creates electrons. These electrons flow to
the more concentrated cell side through the external wire, where they react with Zn2+ ions
and reduce them to Zn(s). This process continues until the concentration of Zn2+ ions
becomes the same in both cells by which the cell potential becomes zero (0). Thus the
highest cell potential is observed when the concentration difference is the highest, which is
at the beginning. Then it decreases to zero as the concentrations in both half-cells becomes
equal.

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PROCEDURE
The instrument employed for measuring emf and the cell potential, is called a multimeter,
which is a digital instrument capable of performing multi-purpose measurements such as
resistance, voltage difference, and current. When the wires are connected to the electrodes,
the voltage generated by the cell can be read directly.

For the construction of Cu / Zn voltaic cell, connect the Cu electrode (cathode) to the V/Ω
terminal of the multimeter and connect the Zn electrode (anode) to the COM terminal of
the multimeter. Adjust the voltage scale to the millivolt scale because of the low voltage
difference that you will read. If the wires are connected in reverse, a negative value on the
multimeter will be displayed. This information can also be used to determine which
electrode is cathode and which electrode is the anode, and consequently in which direction
electrons flow through the external cell circuit.

Salt bridge
Zn strip Cu strip

Multimeter

ZnSO4 solution CuSO4 solution

Figure 12.2 Experimental set-up of the voltaic cell to be constructed

A. Cell Voltage

1. Take 6 clean test tubes.

2. Transfer about 25 mL of 0.50 M CuSO4 into a beaker.

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3. Take 15 mL of 0.50 M CuSO4 from this beaker, using a pipette and transfer into a clean
test tube. Label it as “A”.

4. Take 7.5 mL of 0.50 M CuSO4 from the beaker, using a pipette, and transfer into
another clean beaker and dilute it to 15 mL with distilled water. Transfer this into a
clean test tube and label it as “B”.

5. Take 1.5 mL of 0.50 M CuSO4 from the beaker using a pipette, transfer into another
beaker and dilute it to 15 mL with distilled water. Transfer it into a test tube and
label it as “C”.

6. Repeat the procedure from 2 to 5 for 0.50M ZnSO4. Label the solutions as “D”, “E”
and “F”.

7. At the end, you will have three CuSO4 solutions and three ZnSO4 solutions with
different concentrations.

8. Take test tube “A” containing CuSO4. Bend a sandpapered Cu strip and hang over the
side of the test tube so that it is partly immersed in the solution.

9. Bend the Zn strip and hang it over the side of the test tube “D” containing ZnSO4.

10. Use the crocodile clips to connect the terminals of the multimeter to the metal
electrodes.

11. Construct the salt bridge as described above (Figure 12.2) and immediately read the
initial cell voltage.

WARNING
Immerse the salt bridge as a final step to complete the circuit, then read the
voltage difference.

Dispose your waste into the aqueous waste container.

B. Concentration Effects on Cell Voltage

In order to observe the effect of concentration on the cell voltage, the concentration of the
salt solution in one of the compartments will be changed either by adding successive
amounts of salt or by dilution. In this experiment, dilution of the solution is chosen.

1. Measure the cell potential, Ecell, using the solutions given in Table 12.1 and determine
the effect of concentration change on the cell potential. Write the results in Table 2 in
your report sheet.

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 Table 12.1. Cells constructed for measuring Ecell.

Exp Cu2+(M) Zn2+(M)

1 A D
2 B D
3 C D
4 A E
5 A F
6 C E

C. Concentration Cell

1. Take 3 clean test tubes.

2. Transfer about 25 mL of 2.0 M ZnSO4 into a beaker.

3. Take 15 mL of 2.0 M ZnSO4 from this beaker, using a pipette and transfer into a clean
test tube. Label it as “G”.

4. Take 7.5 mL of 2.0 M ZnSO4 from the beaker, using a pipette, and transfer into
another clean beaker and dilute it to 15 mL with distilled water. Transfer this into a
clean test tube and label it as “H”.

5. Take 1.5 mL of 2.0 M ZnSO4 from the beaker using a pipette, transfer into another
beaker and dilute it to 15 mL with distilled water. Transfer it into a test tube and label
it as “I”.

6. Construct a cell using two zinc strips and two ZnSO4 solutions.

7. Vary the solutions as given in Table 12.2 to construct concentration cells and measure
the cell potential, Ecell.

Table 12.2. Concentration cells constructed

Exp Zn2+ (anode) Zn2+(cathode)

1 H G
2 I G
3 I H

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 CALCULATIONS

A. Cell Voltage
1. Calculate the concentrations of the solutions in test tubes A-F.
2. Write the cathode and anode half reactions and the overall reaction.

B. Concentration Effects on Cell Voltage

1. For the cells given in Table 12.1, calculate Ecell (calculated) using the Nernst
equation and the standard cell potential Eºcell, and then calculate wmax.
Complete Table 1 in your report sheet.

2. Calculate wmax and standard cell potential Eºcell using the experimental Ecell
values by using Nernst equation and compare it with the theoretical value.
Complete Table 2 in your report sheet.

3. Calculate the % error in Ecell and wmax in your measurement for one set of
data.

𝐞𝐱𝐩𝐞𝐫𝐢𝐦𝐞𝐧𝐭𝐚𝐥 𝐯𝐚𝐥𝐮𝐞 − 𝐭𝐡𝐞𝐨𝐫𝐞𝐭𝐢𝐜𝐚𝐥 𝐯𝐚𝐥𝐮𝐞

% 𝐞𝐫𝐫𝐨𝐫 = 𝐱 𝟏𝟎𝟎
𝐭𝐡𝐞𝐨𝐫𝐢𝐭𝐢𝐜𝐚𝐥 𝐯𝐚𝐥𝐮𝐞

C. Concentration Cell

1. Calculate the theoretical cell potentials for each experiment and complete Table 3
in your report sheet.

2. Calculate the % error in Ecell.

Show all of your calculations on back page of the report sheet for one set of data
for each table, separately

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