Chapter 3

Stoichiometry

Introduction

A tremendous number of chemical compounds exists in nature and undergo

myriad reactions. By building and exploiting a systematic understanding of reactivity,
chemists also have produced an impressive array of man-made compounds. The
economics of any chemical process obviously depend on the amounts of each reactant
needed to produce a given amount of product. For processes carried out on an
industrial scale, even very small changes in efficiency can have enormous impact on
profitability. The quantitative relationships between the amounts of reactants and
products in a chemical reaction are referred to as stoichiometry.

Learning Outcomes

At the end of this chapter, you should be able to:

✓ Calculate the amount of product expected from a chemical reaction, given the
amount reactants used.
✓ Calculate the amounts of reactants needed in a chemical reaction to produce
a specified amount of product
✓ Identify a limiting reactant and calculate the amount of product formed from a
non-stochiometric mixture of reactants
✓ Calculate the percentage yield of a chemical reaction

Calculations Based on Balanced Equations

In doing these calculations, we shall use the mole method. The central part of
any calculation of this type is to determine the relative relationships between the moles
of reactants and products from the balanced equation. For example, the equation
representing the burning of methane (CH4) in oxygen to form carbon dioxide and water
is written as follow:

CH4 + 2 O2 CO2 + 2 H2O

 The balanced equation gives us the relationships between moles of methane
and moles of oxygen, moles of methane and moles of carbon dioxide, moles of carbon
dioxide and moles of water, and so on. The following relationships can be obtained
from this balanced equation:

1 mol CH4 = 2 mol O2

1 mol CH4 = 1 mol CO2

1 mol CO2 = 2 mol H2O

and so on.

When considering mass relationships (or weight-weight calculations) from

balanced equation, there are four steps in calculations, although in some problems
some of these are not necessary.

1. Write a complete, balanced equation.

2. Convert from the given units to moles
3. Convert from moles of the given quantity to moles of the desired quantity – from
the balanced equation.
4. Convert from moles of the new quantity to the desired units, using formula
weight, density, Avogadro’s number, and so on.

PROBLEM EXAMPLE 3-1

Calculate the number of moles of NaOH that are necessary to produce moles
of Na2SO4 from the reaction

2 NaOH + H2SO4 Na2SO4 + 2 H2O

SOLUTION

Since the given quantity is in moles and the desired quantity is also in moles,
there is just one step involved – the conversion from moles of NaOH to moles of
Na2SO4, using the relationships from the balanced equation.

2 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻
7.5 mol Na2SO4 x = 15 mol NaOH
1 𝑚𝑜𝑙 Na2SO4
PROBLEM EXAMPLE 3-2

Calculate the number of grams of magnesium chloride that could be obtained

from 8.50 g of hydrochloric acid when the latter is reacted with an excess of
magnesium oxide (MgO).

SOLUTION

The problem involves all four steps: writing the balanced equation, converting
from grams of HCl (hydrochloric acid) to moles, converting from moles of HCl to moles
of MgCl2 (magnesium chloride) using the balanced equation, and converting from
moles of MgCl2 to grams.

The balanced equation is:

MgO + 2 HCl H2O + MgCl2

The calculation is done as follows:

1 𝑚𝑜𝑙 𝐻𝐶𝑙 1 𝑚𝑜𝑙MgCl2 95.3 𝑔 MgCl2

1.5 g HCl x x x = 11.1 g MgCl2
36.5 𝑔 𝐻𝐶𝑙 2 𝑚𝑜𝑙 𝐻𝐶𝑙 1 𝑚𝑜𝑙 MgCl2

QUIZ #3-1

For the reaction

4 FeS + 7 O2 2 Fe2O3 + 4 SO2

a) Calculate the number of moles of Fe2O3 that could be produced from 7.20
moles of FeS.
b) Calculate the number of grams of SO2 that could be produced from 3.25
moles of oxygen.
c) Calculate the number of grams of oxygen that would react with 0.125 g FeS.
d) How many moles of SO2 would be produced if 18.5 g Fe2O3 are produced in a
reaction.
Limiting Reagent

In general, when a chemical reaction is carried out, one of the reagents will be
used in excess of the amount needed. The reagent that is not present in excess is the
one that will determine how much product can be obtained as is thus referred to as the
limiting reagent. For example, in the reaction of hydrogen gas and oxygen gas to
form water: 2H2 + O2 2 H2O , 2 moles of hydrogen will combine with 1 mole
of oxygen to form 2 moles of water. If there is only 1 mole of oxygen present, and an
excess hydrogen, only 2 moles of water can be obtained. No matter how much
hydrogen is present, the oxygen will limit the amount of water that can be produced.
Thus, the oxygen is the limiting reagent.

The following steps can be used in doing calculations of this type:

1. Calculate the number of moles of product that could be obtained for each
reagent given.
2. The reagent that gives the least number of moles of product is the limiting
reagent and is the one that will determine the theoretical yield in the reaction;
that is, no matter how much of the excess reagent is present, no more product
can be obtained than that calculated from the limiting reagent.
3. Next, the moles of theoretical yield are converted to any other desired units,
such as grams.
4. To find the amount of excess reagent present, if desired, we first calculate the
amount of the excess reagent that will be used to produce the theoretical yield.
The difference between this amount and the amount present to start is the
amount of excess. The amount of excess reagent that is used can be
calculated either from the theoretical amount of product attainable, as
calculated in step 2, or from the amount of limiting reagent present. In either
case, the mole relationships from the balanced equation are used to do the
calculation.

PROBLEM EXAMPLE 3-3

A 50.0 g sample of calcium carbonate is reacted with 35.0 g of phosphoric acid.

Calculate:

a) The number of grams of calcium phosphate that could be produced

b) The number of grams of excess reagent that will remain.

SOLUTION
The balanced equation is

3 CaCO3 + 2 H3PO4 Ca3(PO4)2 + 3 CO2 + 3 H2O

a) To calculate the theoretical yield, we first calculate the number of moles of

Ca3(PO4)2 that could be produced by each reagent, if it were used up,

1 𝑚𝑜𝑙 CaCO3 1 𝑚𝑜𝑙 Ca3(PO4)2

50.0 g CaCO3 x x = 0.167 mol Ca3(PO4)2
100 𝑔 CaCO3 3 𝑚𝑜𝑙 CaCO3

1 𝑚𝑜𝑙 H3PO4 1 𝑚𝑜𝑙 Ca3(PO4)2

35.0 g H3PO4 x x = 0.179 mol Ca3(PO4)2
98.0 𝑔 H3PO4 2 𝑚𝑜𝑙 H3PO4

This tells us that CaCO3 is the limiting reagent, and the maximum amount of
product that we can obtain is 0.167 mole of Ca 3(PO4)2. To find the number of
grams that can be produced, we convert 0.167 mole of Ca3(PO4)2 to grams:

310 𝑔𝑟𝑎𝑚𝑠Ca3(PO4)2
0.167 mol Ca3(PO4)2 x = 51.8 g Ca3(PO4)2
1 𝑚𝑜𝑙 Ca3(PO4)2
This is the theoretical yield.

b) To find the grams of excess reagent, we must first find how much of the reagent
that is in excess (H3PO4) is used. Then we subtract this from the amount of
H3PO4 present in the beginning, to find how much excess remains. We can
either start with the theoretical yield [0.167 mol Ca3(PO4)2] and calculate how
much H3PO4 it would take to produce this or start with the limiting reagent (50.0
g CaCO3) and find how much H3PO4 will react with that. Either way, we find
the same result. Let’s start with the 0.167 mol of Ca 3(PO4)2.

2 𝑚𝑜𝑙 H3PO4 98 𝑔 H3PO4

0.167 mol Ca3(PO4)2 x x = 32.7 g H3PO4
1 𝑚𝑜𝑙Ca3(PO4)2 1 𝑚𝑜𝑙 H3PO4
This is the amount of H3PO4 used; therefore, the amount remaining is
35.0 g – 32.7 g = 2.30 g in excess.
 QUIZ #3-2

From 12.5 g of CaCO3 and17.3 g of H3PO4, calculate the number of grams of Ca3(PO4)2
that could be produced from the following equation

3 CaCO3 + 2 H3PO4 Ca3(PO4)2 + 3 CO2 + 3 H2O

Percent Yield

All the calculations that have been done up to this point are theoretical yields.
This is the maximum amount of product that can be obtained in a particular reaction.
In general, however, when these reactions are carried out in the laboratory, we no not
actually obtain the theoretical amount of product. This is especially true in organic
reactions, where there are often side reactions taking place and where some of the
products are lost in the process of isolation and purifications. The amount of products
that is actually obtained is called the actual yield. The percent yield is the percent of
the theoretical yield that is actually obtained, calculated as follows:

𝑎𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
percent yield = x 100
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
PROBLEM EXAMPLE 3-4

If 35.4 g Ca3(PO4)2 is actually obtained in problem example 3-3, what is the

percent yield?

SOLUTION

Actual yield = 35.4 g and theoretical yield = 51.8 g (from problem example 3-3);
therefore

35.4 𝑔
Percent yield = x 100 = 68.3%
51.8 𝑔

PROBLEM EXAMPLE 3-4

If 15.0 g of MgO is treated with 18.5 g of H 3PO4 and 17.6 g of Mg3(PO4)2 is

obtained, calculated the percent yield and the grams of excess reagent.
SOLUTION

The balanced equation is

3 MgO + 2 H3PO4 Mg3(PO4)2 + 3 H2O

a) Find the limiting reagent:

1 𝑚𝑜𝑙 𝑀𝑔𝑂 1 𝑚𝑜𝑙 Mg3(PO4)2

15.0 g MgO x x = 0.124 mol Mg3(PO4)2
40.3 𝑔 𝑀𝑔𝑂 3 𝑚𝑜𝑙 𝑀𝑔𝑂

1 𝑚𝑜𝑙 H3PO4 1 𝑚𝑜𝑙 Mg3(PO4)2

18.5 g H3PO4 x x = 0.0944 mol Mg3(PO4)2
98.0 𝑔 H3PO4 2 𝑚𝑜𝑙 H3PO4

Therefore, H3PO4 is the limiting reagent

b) Calculate the theoretical yield, using the limiting reagent

262.9 Mg3(PO4)2
0.0944 mol Mg3(PO4)2 x = 24.8 g Mg3(PO4)2
1 𝑚𝑜𝑙 Mg3(PO4)2

c) Calculate the amount of excess reagent

using 0.0944 mole Mg3(PO4)2 gives

3 𝑚𝑜𝑙 𝑀𝑔𝑂 40.3 𝑔 𝑀𝑔𝑂

0.0944 mole Mg3(PO4)2 x x = 11.4 g
1 𝑚𝑜𝑙𝑒 Mg3(PO4)2 1 𝑚𝑜𝑙𝑒 𝑀𝑔𝑂
MgO

d) Calculate the percent yield

To do this we use the theoretical yield calculated in step (b) and the actual yield
given in the problem

𝑎𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑 17.6 𝑔

Percent yield = = x 100 = 71%
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑 24.8 𝑔
 QUIZ #3-3

For the reaction

CaO + 2 HCl H2O + CaCl2

1) If 1.23 g of CaO is reacted with excess hydrochloric acid (HCl) and 1.85 g of
CaCl2 is formed, what is the percent yield?
2) If 30.2 g of CaO is added to 34.5 g of HCl and 6.35 g of water is formed, what
is the percent yield?

Chapter 4
Electrochemistry

Introduction

Not only is matter, influenced by electricity but also many of the important
particles of matter are electrical in nature. All atomic nuclei are positively charged, and
all ions are charged either positively or negatively.

Learning Outcomes

After mastering this chapter, you should be able to:

✓ Convert electrical energy to chemical energy in electrolysis cells

✓ Convert chemical energy into electrical energy in galvanic or voltaic
cells
✓ Write anode, cathode and overall reaction equations that take place in
an electrolysis cell.
✓ Calculate equivalent weights and quantitative relationships in
electrolysis cells, in terms of coulombs, amperes, and faradays.
✓ Calculate the effect of concentration has on oxidation or reduction
potentials using the Nernst equation
 LESSON 1
ELECTROLYTIC CELLS

In an electrolytic cell, electrical energy is

used to cause a chemical reaction to take place. An
example of an electrolytic cell is shown at the right.
The substance that conducts the current is molten
sodium chloride. The two electrodes (called the
anode and cathode) are placed into the molten
sodium chloride and an electric current is passed
through it. This electric current consists of a flow of
electrons. Thus, electrons are being force into the
cell. The cation (Na +) moves toward the electrode Figure 1- A simple electrolytic cell
called the cathode. At this electrode, Na + ions accept electrons to form sodium metal
according to the following reaction.

Na + + e - Na

Therefore, reduction (gain of electrons or decrease in oxidation number takes

place at the cathode.

At the other, electrode, called the anode, the anion (Cl -) loses electrons to
form chlorine gas (Cl2) according to the equation

2 Cl - Cl2 + 2 e –

Therefore, oxidation (loss of electrons or increase in oxidation number) takes

place at the anode.

In the cell, electrons move from the anode through the external circuit to the
cathode. The anions move toward the anode, where oxidation takes place. The
cations move toward the cathode where reduction takes place. It must be kept in mind
that these reactions only take place because of the electrical energy being put into the
system. Take note that both oxidation and reduction must take place in the cell. The
electrons lost by one substance must be gained by another.

To write the overall reaction, the cathode reaction must be doubled (or the
1
anode reaction could be written as Cl - Cl2 + e – ), and then the two half-
2

reactions are added together.

Cathode: 2 Na + + 2 e - Na (reduction)

Anode: 2 Cl - Cl2 + 2 e - (oxidation)

Overall: 2 Na + + 2 Cl - 2 Na + Cl2

Besides simple cells like the electrolysis of a cation to a free metal at the
cathode and an anion to a nonmetal at the anode, there are other types of reactions
that can take place at each electrode. Of course, in each case any reaction at the
cathode is reduction and at the anode is oxidation. Consider the following examples.

Anode Reactions (Oxidation)

1. Oxidation of an anion to an element, such as

2 Cl - Cl2 + 2 e –
2. Oxidation of an anion or cation in solution to an ion of higher oxidation state,
such as
Fe 2+ Fe 3+ + e –
3. Oxidation of a metal anode, such as
Cu Cu 2+ + 2e –
4. Oxidation of H2O to produce oxygen:
2 H2 O O2 + 4 H + + 4 e –

Cathode Reactions (Reduction)

1. Reduction of a cation to a metal, such as

Zn 2+ + 2e – Zn
2. Reduction of an anion or cation in solution to an ion of lower oxidation state,
such as
Fe 3+ + e – Fe 2+
3. Reduction of a non-metal to an anion, such as
Cl2 + 2e – 2 Cl –
4. Reduction of H2O to produce hydrogen gas:
2 H2O + 2e – H2 + 2 OH –
 In a particular electrolysis cell there are often several possible reactions that
could take place. For example, in any aqueous solution there is always the possibility
of the water being oxidized or reduced more readily than the cation or anion present.
The electrolysis of aqueous sodium chloride is one case where this takes place. It is
found that hydrogen gas is produced at the cathode and chlorine gas at the anode.
Thus, the overall reaction for this is

2 Na+ + 2 Cl- + 2H2O H2 + Cl2 + 2 OH- + 2 Na+

This is one method that can be used for the commercial preparations for hydrogen and
chlorine, with an aqueous solution of sodium hydroxide as a third product.

As another example, it is found that, upon electrolysis of aqueous sodium

sulfate, hydrogen gas is produced at the cathode and oxygen gas at the anode.
Therefore, the overall reaction here is simply

2 H2 O 2H2 + O2

Electrolysis of water by this method can be accomplished with any solution as long as
the ions in the solution (which must be present in order for electrolysis to take place)
are not oxidized or reduce more readily than water.

Another application of electrolysis cells is in the final purification to obtain pure

copper. In this purification the impure copper acts as the anode and a thin plate of
pure copper acts as the cathode, with the electrolyte being copper (II) sulfate. The
reactions that take place in this electrolysis cell are
Anode: Cu Cu2+ + 2 e –
(from the impure
sample)

Cathode: Cu2+ + 2 e – Cu
(formed (pure)
at the anode)

The copper that forms on the cathode is better than 99.9 % pure. Other metals found
in copper ores, such as silver, gold, and platinum, are deposited as a sludge at the
bottom of the cell and are further refined, and more active metals such as nickel remain
in solution and are later recovered, making the entire operation quite economical. This
process does require considerable amounts of electricity, however, and thus cheap
electrical power must be available near the electrolytic cell plant site.
 LESSON 2
QUANTITATIVE RELATIONSHIPS IN ELECTROLYTIC CELLS

In electrolysis cells, one very important consideration is the amount of electrical

energy necessary for a given amount of material to react. One of the most commonly
used units in expressing amount of electrical energy is the coulomb (coul). Another
very important unit is the faraday (F), which is the amount of energy required for the
flow of 1 mole of electrons. To three significant digits, 1 faraday equals 96,500
coulombs. The unit commonly used to measure current flow is the ampere (A), which
is a rate such that 1 coulomb passes a given point in the circuit in 1 second. Therefore,
A = coul / s, or coulombs = (amperes)(seconds). Keep in mind that a coulomb is an
amount of electrical energy and an ampere is a rate at which it flows.
The equivalent weight, or gram-equivalent weight, of a substance is the mass
in grams that is equivalent to I mole of electrons; that is, it is the amount that reacts
with or is produced by 1 mole of electron. The faraday is therefore the amount of
electrical energy necessary to produce 1 equivalent of pure substance. To determine
the equivalent weight of a substance it is necessary to know how many moles of
electrons are transferred per mole of substance. Therefore, to calculate the equivalent
weight of a substance the formula weight is divided by the number of electrons
transferred.

PROBLEM EXAMPLE 4-1

Calculate the equivalent weight of each of the following:

a) Aluminum
b) Fe, in the reaction Fe Fe2+ + 2 e –
c) Fe, in the reaction Fe3+ + 3 e – Fe
d) Fe, in the reaction Fe3+ + e – Fe2+

SOLUTION

a) Since Al will always lose three electrons to form Al3+, the equivalent weight is
27.0 / 3 = 9.00 g
b) In this case, the equivalent weight of Fe is, 55.8 / 2 = 27.9 g
c) 55.8 / 3 = 18.6 g
d) 55.8 / 1 = 58.8 g
 Since 1 faraday is the amount of electrical energy necessary for the transfer of 1
mole of electrons, it is the amount of electrical energy necessary to produce 1
equivalent of any substance. For example, referring to sample problem 4-1, it
would take 1 F or 96,500 coul to produce 9.00 g of Al, 27.9 g of FeCl 2, and 18.6 g
of Fe from FeCl3. We can also use relationships directly between equivalents and
moles, as follows:

1 mole Al = 3 equivalents Al
1 mole Fe = 2 equivalents Fe (from FeCl2)
1 mole Fe = 3 equivalents Fe (from FeCl3)

PROBLEM EXAMPLE 4-2

How many coulombs would it take to deposit 1.00 g of silver from solution?

SOLUTION

Since Ag is always +1 in compounds, the equivalent weight of Ag is always 108/1 =

108.

1 𝑒𝑞𝑢𝑖𝑣 𝐴𝑔 96,500 𝑐𝑜𝑢𝑙

1.0 g Ag x x = 894 coul
108 𝑔 𝐴𝑔 1 𝑒𝑞𝑢𝑖𝑣 𝐴𝑔

PROBLEM EXAMPLE 4-3

How many grams of Zn could be deposited by 96.5 coul?

SOLUTION

Equivalent weight of Zn = atomic weight / 2 = 65.4 / 2 = 32.7

1 𝑒𝑞𝑖𝑣 𝑍𝑛 32.7 𝑔 𝑍𝑛
96.5 coul x x = 3.27 x 10-2 g Zn
96,500 𝑐𝑜𝑢𝑙 1 𝑒𝑞𝑢𝑖𝑣 𝑍𝑛

PROBLEM EXAMPLE 4-4

How long would it take a current of 100 A to deposit 10.0 g of Fe from a

solution of FeCl2?

SOLUTION

100 A = 100 coul / s

Equivalent weight of Fe in FeCl2 = 55.8 / 2 = 27.9

1 𝑒𝑞𝑢𝑖𝑣 𝐹𝑒 96,500 𝑐𝑜𝑢𝑙 1𝑠

10.0 g Fe x x x = 346 s
27.9 𝑔 𝐹𝑒 1 𝑒𝑞𝑢𝑖𝑣 𝐹𝑒 100 𝑐𝑜𝑢𝑙

PROBLEM EXAMPLE 4-5

How many grams of Al could be obtained by a current of 20 A flowing for 1

hr?

SOLUTION

60 𝑚𝑖𝑛 60 𝑠
1 hr x x = 3600 s
1 ℎ𝑟 1 𝑚𝑖𝑛

Since coul = A x s, the number of coulombs is

(20 A)(3600 s) = 72,000 A-s = 72,000 coul

1 𝑒𝑞𝑢𝑖𝑣 𝐴𝑙 9.00 𝑔 𝐴𝑙
72,000 coul x x = 6.7 g Al
96,000 𝑐𝑜𝑢𝑙 1 𝑒𝑞𝑢𝑖𝑣 𝐴𝑙

QUIZ #4-1

1. Calculate the equivalent weight of Sn for the reaction

Sn Sn 2+ + 2 e –
2. Calculate the equivalent weight of I2 for the reaction
2I- I2 + 2 e –
3. Calculate the number of grams of aluminum that could be deposited by
a) 5,000 coul
b) a current of 100 A flowing for 10 minutes
4. Calculate the time, in seconds, that it would take
a) for a current of 50.0 A to deposit 18.5 g of zinc
b) for a current of 18.5 A to form 42.0 g of iron from a solution of iron (III)
chloride (Fe3Cl)
5. Calculate the number of amperes necessary to
a) deposit 125 g of silver in 3.50 hours
b) deposit 84.5 g of nickel from a solution of NiCl3 in 45.0 minutes
6. Calculate the number of coulombs necessary to
a) Plate out 18.5 g of chromium from a solution of Cr2(SO4)3
b) Plate out 245 mg of tin from a solution of Sn(NO3)2
 LESSON 3
VOLTAIC OR GALVANIC CELLS

In a voltaic or galvanic cell, a chemical reaction produces electrical energy. In

a cell of this type, the oxidation-reduction reaction is carried out in such a way that the
electrons being transferred from the reducing agent to the oxidizing agent travel
through a wire and thus produce an electric current.

One example of a voltaic cell involves zinc metal in a solution containing Cu2+
ions. The overall reaction that takes place is

Zn + Cu2+ Zn2+ + Cu

If the reaction is carried out in such a way that the zinc metal does not come in
contact with the Cu2+ ions, the energy given off may be obtained as electricity. This is

Figure 2- A simple voltaic cell using (a) a porous partition and (b) a salt bridge

done in a cell like that shown in the Figure 3. In this cell, the solution containing the
Cu2+ ions are separated from the solution in which the zinc metal is placed. The two
solutions are separated by a porous plate.as shown if Figure 3a. They can also be
separated by a salt bridge, which contains an ionic substance and allows ions to pass
from a solution in one container to a solution in another container, as shown in Figure
3b. When switch in the external circuit is closed, the reaction will begin to take place
since electrons can then pass through from the anode to the cathode. The two half-
reaction that take place are

Anode: Zn Zn2+ + 2 e – (oxidation)

Cathode: Cu2+ + 2 e – Cu (reduction)

 LESSON 4
STANDARD ELECTRODE POTENTIALS

The electromotive series of metals, or sometimes the activity series, tells us

that any metal will displace a lower metal from a solution of its ions. The basis of the
series is the standard electrode potentials (Eo) as shown in Table 4-1. These give the
potential, in volts, for a particular half-reaction to take place. The potentials given in
Table 4-1 are written as reduction potentials, where each half-reaction is written as
a reduction reaction. If these were written as oxidation potentials, the reaction would
be the reverse of that given, and the sign would be opposite. For example, for the
oxidation half-reaction, Li Li+ + e –, the potential (Eo) is + 3.04 volts (V).

Table 4-1. Standard reduction potentials for some common metals - for aqueous solutions
of ions at 1.0 M concentration at 25oC and H2 gas at 1.0 atm pressure and 25oC

It is not possible to measure the potential for any half-reaction by itself, it can
only be measured as compared to something else. Thus, each of these is compared
to the 2 H+ + 2 e – H2 half reaction; that is, this half-reaction is considered
to have a standard potential of 0.00 (at 25 oC and 1 atm pressure). Then all the other
half-reactions are compared to this. The cell used to carry this out is shown in Figure
4.Figure 3 - Cell used to measure standard potentials
 The metal in a solution containing its ions is used as one electrode and the
hydrogen gas being passed over platinum metal is the other electrode. Either the
reaction of metal ion going to metal ion (M n+ + n e – M) or metal going to
metal ion (M M s n+ + n e –) will take place, and the voltage is measured.
For example, if the Zn – Zn 2+
half-cell is used for the electrode, the Zn goes to Zn 2+

2+
and the potential is 0.76 V; therefore, the potential for the reverse reaction (Zn + 2
e– Zn) is -0.76 V, (as compared to the hydrogen electrode) as given in the
2+
Table. If Cu and Cu ion are used as the other electrode, along with the hydrogen
2+ –
electrode, the reduction half-reaction ( Cu + 2e Cu) takes place and
produces a potential of 0.34 V (as compared to the hydrogen electrode). In all these
cells the concentration of the ions is 1.0 M, which is taken as the standard. Thus, the
potentials given here are called standard electrode potentials or, for the particular
values given in the table, standard reduction potentials.

To determine if an oxidation-reduction reaction will take place spontaneously,

the two half-reactions are written and the potentials are added. If the potential is
positive the reaction will go spontaneously; if it is negative, it will not. Consider the
following examples (all concentrations 1.00 M):

1. Mg 2+ + Zn Zn 2+ + Mg
Mg 2+ + 2 e – Mg Eo = -2.36 V
Zn Zn 2+ + 2 e – Eo = +0.76 V
Mg 2+ + Zn Mg + Zn 2+ Eo = -1.60 V

Therefore, this reaction will not go spontaneously as written (the reverse reaction
would since the potential would be + 1.60 V)
 2. 3 Mg + 2 Al 3+ 3 Mg 2+ + 2Al
3 (Mg Mg 2+ + 2 e –) Eo = +2.36 V
2(Al 3+ + 3e– Al) Eo = -1.66 V
3 Mg + 2 Al 3+ 3 Mg 2+ + 2 Al Eo = +0.70

This reaction will go spontaneously as written. (The potential is not multiplied by

3 or 2 in the half-reactions)

Calculations of this type not only tell what reactions will go spontaneously but
also tell us something about the reverse reaction; that is, in the first example the given
reaction will not go spontaneously but the reverse reaction would.

QUIZ #4-2

1. Calculate the voltage that would be developed by cells using the following
reactions (all concentrations 1M). Use Table 4.1
a) Zn + Ni 2+ Zn 2+ + Ni
b) Pb + Zn 2+ Pb 2+ + Zn
2. From the standard reduction potentials for metals (Table 4.1), determine
whether the following reactions will occur
a) Zn + Ni 2+ Zn 2+ + Ni
b) Pb + Zn 2+ Pb 2+ + Zn

LESSON 5
THE NERNST EQUATION

All the potential used in the previous lesson involved solutions in which the
concentration of the ions was 1 M. This is known as the standard state. As the
concentration changes, the potential for the half-reaction also changes according to
the Nernst equation, which states that

0.059 [𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠] 𝑥
E = Eo - log
𝑛 [𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠] 𝑦

where Eo = the standard oxidation or reduction potential

 N = the number of electrons transferred

x and y = the coefficients in the balance equation

0.059 = a constant at 25 oC

In using this equation it is very important always to write the log factor as the
concentration of products over reactants, just as in equilibrium constants, for the
reaction as written; that is, if Eo is an oxidation potential (from the reduced to oxidized
state, often written as Eored, ox) it is [oxidized state]/[reduced state]. And if Eo is a
reduction potential (Eored, ox) it is [reduced state/oxidized state].

For anything in the free state, such as a free metal (M o), the concentration is
taken as one. It is actually the activity that is one but most purposed molar
concentration of one is practically the same.

PROBLEM EXAMPLE 4-6

Calculate the half-cell potential for the reaction

Cu 2+ + 2 e- Cuo

When the [Cu 2+] is 1 x 10 -4

SOLUTION

Since the [Cu 2+] is less than one, we would expect the potential to decrease (whether
it is a positive or a negative value, it should become smaller). The value of E o for this
half-reaction is +0.34 V (from Table 4-1). The Nernst equation is

0.059 [𝐶𝑢𝑜 ]
o
E=E - log
2 [𝐶𝑢2+]

Putting the known values into this (recall that [Cuo] = 1) gives

0.059 1
E = 0.34 - log
2 1 𝑥 10−4

0.059
E = 0.34 - ( ) (4)
2

E = 0.22 V This value is less than 0.34, as predicted

PROBLEM EXAMPLE 4-7

For the reaction 2 Al + 3 Cu 2+ 2 Al 3+ + 3 Cu, calculate the potential

if the [Cu 2+] is 1 x 10 -4 and the [Al 3+] is 1 x 10 -3

SOLUTION

This can be solved either as two separate steps or as the overall reaction.

0.059 1
a) EAl, Al3+ = 1.66 – log = 1.66 + 0.059 = 1.72 V
3 1 𝑥 10−3

0.059 1
ECu2+,Cu = 0.34 - log = 0.34 – 0.118 = 0.22 V
2 1 𝑥 10−4

Eoverall = 1.72 V + 0.22 V = 1.94 V

In this case, it is not nec

THE PERIODIC TABLE
References:

Lawrence S. Brown and Thomas A. Holme, Chemistry for Engineering Students,

2nd ed. Cengage Learning Asia Pte Ltd., 2012

Stanley E. Manahan, The Geosphere and Geochemistry in ‘Environmental

Chemistry’, 8th Edn., CRC Press, 2005

Manahan, Stanley E. “Environmental Science, Technology, and Chemistry”

Environmental Chemistry, 2000

National Research Council, Setting Priorities for Drinking Water, National Academy
Press, Washington, D.C., 1999.

Carl H. Snyder; Chemicals, Pollution, and the Environment, the meaning of pollution,
in The Extraordinary Chemistry of Ordinary Things, third edition, John Wiley &
Sons, Inc, 1998

Howard, Alan G., Aquatic Environmental Chemistry, Oxford University Press,

Oxford, UK, 1998.

Murray N. McBride; Environmental Chemistry of Soils, Oxford university press Inc,

1994

J. Greyson, Carbon, Nitrogen and Sulfur Pollutants and Their Determination in

Air and Water. New York: Marcel Dekker, 1990

Fred H. Redmore, Fundamentals of Chemistry, Apson Enterprises, 1980

Environmental Chemistry, http://www.chem1.com/chemed/digtexts.shtml

Environmental Issues, http://www.elmhurst.edu/~chm/vchembook/index.html
Water Pollution and Society, http://www.umich.edu/~gs265/society/waterpollution.htm
Environmental Issues, http://www.elmhurst.edu/~chm/vchembook/index.html
Water Structure and Behavior, http://textbookrevolution.org/chemistry/water-structure-
and-behavior