Standard:

Work Sheet ( …………………………… )

1 – Choose the correct answer :

Choose the correct answer :
1-Substances that conduct electric current through the movement of its ions are
conductors ……….‫المواد التي توصل التيار الكهربي من خالل حركة األيونات هي‬
( metallic‫ – فلزية‬electrolytic‫ – إلكتروليتية‬electronic‫) إلكترونية‬

2- CuSO4 + Zn → …. + …..

a- CuSO4 + Zn
b- Cu + Zn SO4
c- CuS + Zn O4

3- The activity series has long been used to ……‫متسلسلة النشاط الكيميائي تستخدم في‬
a - predict the direction of oxidation-reduction reactions
b – arrange the elements according to its ch. Activity.
C - The electrode at which reduction process occurs in galvanic cells is………….

4 -The standard hydrogen electrode has value of ……‫ قياس قطب الهيدروجين القياسي‬.
( zero – positive one – negative one ) .
5 - If the standard reduction potentials for zinc and nickel were 0.76 and –0.23 volts ,
respectively - , thus e.m.f for the cell is …………. Volt
‫فإن القوه الدافعة الكهربية لهذه‬0.23 – ‫ و‬0.76 ‫إذا كانت قيمه جهد اإلختزال لكل من الزنك والنيكل علي التوالي‬
‫ الخليه هـو‬................
( (0.99 ) - ( 0.76) - ( 0.53) ) .

1
6- Electrochemicalic cells can obtain electric current as a result of ……………
‫تنتج تيار كهربي نتيجة‬ ‫ الخاليا الكهروكميائية‬..................
A -spontaneous oxidation – reduction reaction. ‫تفاعل األكسدة واإلختزالـ‬
B - oxidation reaction. ‫تفاعل األكسدة‬
C - reduction reaction. ‫تفاعل اإلختزال‬

2 – Complete :
A - emf of cell = ………….. - ……………………
1 - potential of Cathode - potential of anode
2 - potential of Cathode + potential of anode
3- potential of anode
B-

Homework (purification of copper)

1 – Complete :‫اكمل‬
1 - The copper ion attract to the ……………pole .‫ أيون النحاس ينجدب نحو القطب‬..
2 - Copper ion carry ……. Charge . …………… ‫ أيون النحاس يحمل شحنة‬.

Cell potentials and the electromotive series

 

It has long been known that some metals are more

"active" than others in the sense that a more active
metal can "displace" a less active one from a solution of
its salt. The classic example is the one we have already
mentioned on the preceding page:

2
 Zn(s) + Cu2+→ Zn2+ + Cu(s)

Here zinc is more active because it can displace (precipitate) copper from solution. If
you immerse a piece of metallic zinc in a solution of copper sulfate, the surface of the
zinc quickly becomes covered with a black coating of finely-divided copper, and the blue
color of the hydrated copper(II) ion diminishes.

Similar comparisons of other metals made it possible to arrange them in the order of
their increasing electron-donating (reducing) power. This sequence became known as
the electromotive or activity series of the metals.

Li 2 Li(s) + 2 H2O( ) → 2 LiOH(aq) + H2(g) The most active (most strongly

displace H2 reducing) metals appear on top,
from water, K 2 K(s) + 2 H2O( ) → 2 KOH(aq) + H2(g)
steam, or and least active metals appear on
Ca Ca(s) + 2 H2O( ) →Ca(OH)2(s) + H2(g)
acids the bottom. A more active metal
Na 2 Na(s) + 2 H2O( ) → 2 NaOH(aq) + H2(g) (such as Zn) will donate electrons
Mg Mg(s) + 2 H2O(g) → Mg(OH)2(s) + H2(g) to the cation of a less active metal
Al 2 Al(s) + 6 H2O(g) → 2 Al(OH)3(s) + 3 H2(g) (Cu2+, for example.)
displace H2
from steam or Mn Mn(s) + 2 H2O(g) →Mn(OH)2(s) + H2(g)
acids Notice the special role of hydrogen
Zn Zn(s) + 2 H2O(g) → Zn(OH)2(s) + H2(g)
here; although H2 does not have
Fe Fe(s) + 2 H2O(g) → Fe(OH)2(s) + H2(g) the physical properties of a metal,
Ni Ni(s) + 2 H+(aq) → Ni2+(aq) + H2(g) it is capable of being "displaced" (a
displace H2 Sn Sn(s) + 2 H+(aq) → Sn2+(aq) + H2(g) rather archaic term seldom used in
from acids modern chemistry) from H2O or H+-
only
Pb Pb(s) + 2 H+(aq) → Pb2+(aq) + H2(g) containing (acidic) solutions. Note
that the "active" metals are all
H2 "attacked by acids"; what this
really means is that they are
Cu capable of donating electrons to H+.

can't displace Ag
H2
 
Pt

Au (This table was adapted from a now-

disapeared one at General Chemistry
Online .)

The activity series has long been used to predict the direction of oxidation-reduction
reactions; see here for a nicely-done table with explanatory material. Consider, for
example, the oxidation of Cu by metallic zinc that we have mentioned previously. The
fact that zinc is near the top of the activity series means that this metal has a strong
tendency to lose electrons. By the same token, the tendency of Zn to accept electrons is
relatively small. Copper, on the other hand, is a poorer electron donor, and thus its
oxidized form, Cu, is a fairly good electron acceptor. We would therefore expect the
reaction

Zn(s) + Cu2+→ Zn2+ + Cu(s)

3
 to proceed in the direction indicated, rather than in the reverse direction. An old-
fashioned way of expressing this is to say that "zinc will displace copper from solution".

The above table is of limited practical use because it does not take into account the
concentrations of the dissolved species. In order to treat these reactions quantitatively,
it is convenient to consider the oxidation and reduction steps separately.

Standard half-cell potentials

When a net reaction proceeds in an electrochemical cell, oxidation occurs at one
electrode (the anode) and reduction takes place at the other electrode (the cathode.)
We can think of the cell as consisting of two half-cells joined together by an external
circuit through which electrons flow and an internal pathway that allows ions to migrate
between them so as to preserve electroneutrality.

Reduction potentials

Each half-cell has associated with it an electrode-solution potential difference whose

magnitude depends on the nature of the particular electrode reaction and on the
concentrations of the dissolved electroactive species. The sign of this potential difference
depends on the direction (oxidation or reduction) in which the electrode reaction
proceeds. In order express them in a uniform way, we adopt the convention that half-
cell potentials are always defined for the reduction direction. Thus the half-cell potential
for the Zn/Zn2+ electrode (or couple as it is sometimes called) always refers to the
reduction reaction

Zn2+ + 2e–→ Zn(s)

In the cell Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s) the zinc appears on the left side, indicating that it is being
oxidized, not reduced. For this reason, the potential difference contributed by the left half-cell has the opposite
sign to its conventional half-cell potential. More generally, we can define the cell potential or cell EMF as

Ecell = ΔV = Eright – Eleft (1)

in which "right" and "left" refer to the cell notation convention ("reduction on the right")
and not, of course, to the physical orientation of a real cell in the laboratory. If we
expand the above expression we see that the cell potential

Ecell = VCu – Vsolution + Vsolution – VZn

is just the difference between the two half-cell potentials Eright and Eleft.

Reference half-cells

The fact that individual half-cell potentials are not directly measurable does not prevent
us from defining and working with them. Although we cannot determine the absolute
value of a half-cell potential, we can still measure its value in relation to the potentials of

4
other half cells. In particular, if we adopt a reference half-cell whose potential is
arbitrarily defined as zero, and measure the potentials of various other electrode
systems against this reference cell, we are in effect measuring the half-cell potentials on
a scale that is relative to the potential of the reference cell.

The reference cell that has universally been adopted for this purpose is the hydrogen
half-cell

Pt | ½ H2(g) | H+(aq) || ...

in which hydrogen gas is allowed to bubble over a platinum electrode having a specially
treated surface which catalyzes the reaction

½ H2(g)→ H+ + e–

When this electrode is operated under standard conditions of 1 atm H 2 pressure, 25°C,
and pH = 0, it becomes the standard hydrogen electrode, sometimes abbreviated SHE.

In order to measure the relative potential of some other electrode couple M 2+/M, we can
set up a cell

Pt | H2(g) | H+ || M2+(aq) | M(s)

whose net reaction is

H2(g) + M2+(aq)→ 2H+ + M(s)

the potential difference between the platinum and M electrodes will be

Ecell = VM – Vsolution + Vsolution – V Pt

but since the difference Vsolution – V Pt is by definition zero for the hydrogen half-cell, the
cell potential we measure corresponds to

Ecell = VM – Vsolution

which is just the potential (relative to that of the SHE) of the half-cell whose reaction is

M2+ + 2e–→ M(s)

Measurement of a standard reduction potential.

The M2+/M half-cell is on the left, and the standard hydrogen cell is on the
right. The two half-cells are joined through the salt bridge in the middle.
The more "active" the metal M (the greater its tendency to donate electrons
to H+), the more negative will be Ecell = ΔV = Eright – Eleft

5
  

Standard [reduction] potentials are commonly denoted by the symbol E°. E° values for
hundreds of electrodes have been determined (mostly in the period 1925-45, during
which time they were referred to as "oxidation potentials") and are usually tabulated in order of
increasing tendency to accept electrons (increasing oxidizing power.)

Table 2: some standard reduction

potentials oxidant reductant
E°, volts
(electron acceptor) (elecron donor)
A much more extensive table can be
Na+ Na(s) –2.71
found here. Note particularly that 2+
Zn Zn(s) –.76
 Unlike the activity series mentioned Fe2+ Fe(s) –.44
above, this table includes non- Cd2+ Cd(s) –.40
metallic substances, and it is
quantitative.
Pb2+ Pb(s) –.126
2 H+ H2(g) 0.000
 The more positive the half-cell EMF,
the greater the tendency of the AgCl(s) Ag(s) + Cl–(aq) +.222
reductant to donate electrons, and Hg2Cl2(s) 2Cl–(aq) + 2Hg( ) +.268
the smaller the tendency of the
Cu2+ Cu(s) +.337
oxidant to accept electrons.
I2(s) 2 I– +.535
 A species in the leftmost column can
act as an oxidizing agent to any Fe3+ Fe2+ +.771
species above it in the reductant Ag+ Ag(s) +.799
column. O2(g) + 4H+ 2 H2O( ) +1.23
 Oxidants such as Cl2 that are below Cl2(g) 2 Cl– +1.36
H2O will tend to decompose water.

Given the E° values for two half reactions, you can easily predict the potential difference
of the corresponding cell: simply add the reduction potential of the reduction half-cell to
the negative of the reduction potential (that is, to the oxidation potential) of the
oxidation reaction.

6
Problem Example 1

Find the standard potential of the cell

Cu(s) | Cu2+ || Cl– | AgCl(s) | Ag(s)

and predict the direction of electron flow when the two electrodes are connected.

Solution: The net reaction corresponding to this cell will be

2 Ag(s) + 2 Cl–(aq) + Cu2+(aq)→AgCl(s) + Cu(s)

Since this involves the reverse of the AgCl reduction, we must reverse the corresponding half-
cell potential:

Ecell = (.337 – .222) v = .115 v

Since this potential is positive, tthe reaction will proceed to the right; electrons will be withdrawn
from the copper electrode and flow through the external circuit into the silver electrode. Note
carefully that in combining these half-cell potentials, we did not multiply E° the for the Cu2+/Cu
couple by two. The reason for this will be explained later.

Try to solve worksheet ( ) with your teacher

=======================================================
==================================================

Define standard electrode potentials relative to the standard hydrogen electrode and
describe methods used to measure the standard electrode potentials of metals or non-
metals in contact with their ions in aqueous solution. Calculate a standard cell potential
by combining two standard electrode potentials.

The cell potential of an electrochemical cell:

We saw in a previous section that the redox reaction

7
 can be exploited to create an electrochemical cell which is written conventionally as

The cell potential (emf) of this cell under standard conditions is 1.10 V (volt). Further, the electrons
flow in the external circuit from the anode (Zn), where oxidation takes place, to the cathode (Cu),
where reduction occurs.
Now consider the two half-reactions which contribute to the cell, written down as reductions (gain
of electrons):

Since the cell causes electrons to flow in the external circuit from Zn to Cu, it means that reaction
(2) takes place rather than reaction (1). Reaction (2) takes place because the REVERSE of reaction
(1) supplies the 2 electrons required.
The emf of the cell (1.10 V) is the POTENTIAL DIFFERENCE between the electrodes of the cell,
which is the difference between the abilities of the half-cells to attract electrons.

We could therefore write down the emf of the above cell (under standard conditions) as:
emf of cell = potential of Cu - potential of Zn
or conventionally

and (anode) are the STANDARD ELECTRODE POTENTIALS of the cathode and the anode
(cathode)
respectively. Since these represent the ability of the electrode to accept electrons, they are in fact
REDUCTION POTENTIALS.
is the emf of the cell, which can be determined by actually constructing the cell and
(cell)
measuring its potential (in volt).
8
 In principle, any redox reaction could be utilised to make an electrochemical cell. For example, one
could use the reaction

to construct the cell

and this cell could be shown experimentally to have an emf of 1.24 V at a temperature of 25 ‫؛‬C.
If one only knew the values of the standard potentials of the half-reactions adding up to the whole
redox process, one could easily calculate the emf of any cell using the formula

It is not possible to determine the absolute values of the electrode potentials. We can however
determine the values of half-reactions relative to a standard electrode whose value is set
arbitrarily at 0.00 V.
The standard hydrogen electrode:
Consider the half-reaction

and let us use it to construct the electrochemical cell

This cell has an experimentally determined of 0.34 V at 25 ‫؛‬C. If we assign a standard electrode
potential of 0.00 V to the hydrogen half-reaction (which is the anode reaction in this case),

Now let us look at the cell

9
 This cell has = -0.76 V at 25 ‫؛‬C. (Normally, a negative emf means the anode and cathode have
been wrongly identified. As the cell is written, electrons should flow from H 2 to Zn, but in fact it is
the other way round!)
However, by convention, the standard hydrogen electrode is always written on the left-hand side
of the cell. In other words, we always write such cells as if the standard hydrogen electrode were
the anode. Thus ,

Note that a hydrogen half-cell is constructed by bubbling pure H 2 gas over a piece of platinum foil
connected to the external circuit. This enables contact to be made between the gas and the
solution. For this reason, the standard hydrogen half-cell is normally written

A typical cell involving a hydrogen half-cell is

shown on the left. The half-cell whose E is
measured is the left hand electrode. The hydrogen
gas is at a pressure of 101.3 kPa.
In this way one can derive the values for a wide
variety of half-reactions. In the examination you
will normally be supplied with a table of standard
electrode potentials, so do not try to memorise
any of them, except the one for the reduction of
H2, which is easy to remember, as it is simply 0.00
by definition!
Note that a metal which has a lower electrode potential will displace from solution a metal which
has a higher electrode potential.

Try to solve worksheet ( ) with your teacher

10
11