Galvanic, Voltaic and Daniell Cell Reactions

A galvanic cell is also referred to as a voltaic cell or Daniell cell. The common
household battery is an example of a galvanic cell. The flo of electrons from
one chemical reaction to another happens through an outside circuit resulting in
current. Current is measured in amperes !A" and is a measure of the number of
electrons that flo past a certain point in the circuit at any given moment.
This is a simple redox reaction in hich both cells are combined into one. There
is a flo of electrons but not through an outside circuit.
#ne half of the cell is separated from the other by a porous barrier, sometimes
called a semi$permeable barrier or by a physical salt bridge li%e in the diagram
belo. The metal strips are referred to as electrodes and the dissolved salt
solutions are electrolytes.
To help remember hich electrode does hat use the chemist&s mnemonic term
'R(DCAT'
i.e. Reduction!R(D" occurs at the cathode!CAT", and oxidation occurs at the
anode, but only in an (lectrolytic cell in and Galvanic cell the positions are
reversed.
#xidation occurs at the cathode and reduction at the anode.
This is the chemical ay of loo%ing at it.
)hysics people ill tell you the cathode is positive!*ve" and the anode is
negative !$ve" and electrons flo from the anode to the cathode through an
external circuit.
Do you see the inherent conflict beteen these to statements+
,f reduction occurs at the cathode, then the cathode must have the surplus of
electrons, but it-s labeled as being positive !*ve". ,f the cathode as the surplus
then the anode must be deficit in electrons yet it is labeled as negative !$ve".
.hy is this+++
,t comes from the old cause and effect concept. .e are used to loo%ing at the
flo of electrons !electricity" that e almost never stop to see hat caused the
flo to happen. This is here the science of chemistry comes in.
The reasons behind electron flo don&t start ith the flo of electrons. ,t starts
ith / metals, one being stronger in its desire for electrons than the other. !i.e.
bending trees don&t cause the ind to blo either"
0et-s see if e can clarify this1
2. The metal ith the stronger desire for electrons3 i.e. the higher
electronegativity, is the one that ill be reduced. The metal ions in the electrolyte
steal electrons from the metal strip. This causes the metal ions to become
reduced to the metal atom. The strip of metal, having lost electrons becomes
more positive.
/. The deficit of electrons at the cathode means that there is no a surplus of
electrons at the anode. i.e. The anode is no negative hen compared to the
cathode. !This is the physics point of vie"
4. (lectrons flo from the $ve anode to the *ve cathode to replace those
electrons lost to the reduction reaction.
5. As the electron 6uantity at the anode drops there is an attraction for electrons
in the electrode. As electrons get removed from the electrode, metal atoms in the
electrode give up their electrons, becoming positive ions, and these positive ions
dissolve off into the electrolyte solution.
7. ,f the salt bridge is not there, the cell that is performing the reduction ould
become very negative, because the negative anion must remain hile all the
positive cations are being reduced. The cell that is performing the oxidation ill
become very positive, because of the formation of positive ions. (ventually this
buildup ould stop the reactions since the positive cell ould build up such a
large positive charge that it ould start to become more attractive to the electron
flo that the original cathode metal electrode. At the same time the buildup of
the large negative charge in the cathodic cell ould start to repel or oppose the
flo of electrons. A salt bridge beteen the to cells allos a balancing of the
electrolytes so that this buildup does not ta%e place. The negative anions from
the reduction cell react ith the positive cations produced in the oxidation cell
neutrali8ing their charges.
To obtain the overall reaction that ta%es place in the electrochemical cell, the cell
reaction, simply add the individual electrode reactions together. 9efore doing this
ma%e sure that the number of electrons gained is e6ual to the number of electrons
lost. This is a re6uirement that every redox reaction must obey. :ultiply the half$
reactions by a common multiple in order to achieve this e6ual number.
;a
*
!a6" * e

< ;a!s" !cathode"

Cl

!l" < Cl/!g" * /e

!anode"
/ ;a
*
!l" * / Cl

!l" * /e

< / ;a!l" * Cl/!g" * /e

!cell reaction"
Then finish the reaction by canceling out li%e terms on either side of the $$$$$=.
The overall cell reaction is therefore1 / ;a
*
!l" * / Cl
$
!l" $$= / ;a!l" * Cl/ !g"
>tandard Cell Reduction )otentials
The voltage across the electrodes of a galvanic cell can be attributed to the
difference in the tendencies of the two half-cells to undergo reduction.
Voltage or electromotive force (emf) can easily be thought of as the force ith
hich an electric current is pushed through a ire. ,t is measured in terms of an
electrical unit called the volt (V). Voltage is a measure of the amount of energy
that can be delivered by a coulomb of electrical charge as it passes through a
circuit. A current floing under an emf of 2 volt can deliver 2 ?oule of energy
per coulomb.
2 V @ 2 ABC
The maximum emf of a galvanic cell is called the cell potential, (cell. ,t is
measured ith a device that dras negligible current during the experiment. (cell
depends on the composition of the electrodes and the concentrations of the ions
in each of the half$cells.
Cor reference purposes, the standard cell potential, symboli8ed (
o
cell, is the
potential of the cell hen all of the ion concentrations are 2.DD :, the
temperature is /7
o
C, and any gases that are involved in the cell reaction are at a
pressure of 2 atm.
Cell potentials are rarely larger than a fe volts. Cor example, the standard
potential for the galvanic cell constructed from silver and copper electrodes
produces only about D.5E V, and one cell in an automotive battery produces only
about / V. 9atteries that generate higher voltages contains a number of cells
ired in series so that their emfs are additive.

Reduction )otentials
,t is useful to imagine that the measured overall cell potential arises from a
competition beteen the to half$cells for electrons. ,f e thin% of each half$
cell reaction as having a certain natural tendency to proceed as a reduction, the
magnitude of hich is expressed by its reduction potential or standard reduction
potential hen the temperature is /7
o
C, concentrations are 2 :, and the pressure
is 2 atm. .hen to half$cells are connected, the one ith the larger reduction
potential $ the one ith the greater tendency to undergo reduction $ ac6uires
electrons from the half$cell ith the loer reduction potential, hich is therefore
forced to undergo oxidation. The measured cell potential actually represents the
magnitude of the difference beteen the reduction potential of one half$cell and
the reduction potential of the other. ,n general,
(
o
cell @ !standard reduction !standard reduction
potential of the potential of the
substance reduced" substance oxidi8ed"
0et&s loo% at the silver$copper cell. Crom the cell reaction
/ Ag
*
!a6" * Cu!s" < Cu
/*
!a6" * / Ag!s"
e can see that the silver ion is reduced and copper is oxidi8ed. ,f e compare
the to possible reduction half$reactions,

Ag
*
!a6" * e
$
< Ag!s"
Cu
/*
!a6" * / e
$
< Cu!s"
the one for Ag
*
must have a greater tendency to proceed than the one for Cu
/*
,
because it is the silver ion that is actually reduced. This means that the standard
reduction potential of Ag
*
, (
o
Ag
*
, must be larger than the standard reduction
potential of Cu
/*
, (
o
Cu
/*
. ,f e %ne the values of (
o
Ag
*
and (
o
Cu
/*
, e could
calculate (
o
cell thusly1
(
o
cell @ (
o
Ag
*
(
o
Cu
/*

Assigning >tandard Reduction )otentials
)otentials are assigned hen a cell is compared against a hydrogen half cell.
>ome cells li%e the fluorine half cell are reduced more easily than hydrogen
therefore the reduction potential of fluorine compared to hydrogen as */.FE V.
At the other end of the scale, lithium does not li%e to reduce compared to
hydrogen, hydrogen is more easily reduced so 0i is oxidi8ed and has a potential
voltage of $4.D7 V.
Gsing a list of standard reduction potentials, you can 6uic%ly and easily calculate
the (
o
cell for any pair of possible half$cells under normal conditions.
Gsing >tandard Reduction )otentials
The %ey to this using standard reduction potentials is to remember that1

The more positive reduction potential occurs as a reduction
The half$cell reactions and their standard reduction potentials from a >tandard
Reduction Table can be used in a number of ays to give information about
galvanic cells. (6ually useful is the fact that they can provide information about
the outcome of redox reactions, hether they occur in a galvanic cell or not. The
example belo shos hoe reduction potentials can be sued to predict the
standard cell potential and the overall reaction in a galvanic cell.
e.x. A galvanic cell as constructed using electrodes made of lead and lead!,V"
oxide !)b#/" ith sulfuric acid as the electrolyte. The half$cell reactions and
their reduction potentials in this system are1
)b#/!s" * 5H
*
!a6" * >#5
/$
!a6" * /e
$
)b>#5!s" * / H/# (
o
)b#/ @ 2.EI V
)b>#5!s" * /e
$
)b!s" * >#5
/$
!a6" (
o
)b>#5 @ $D.4E V
.hat is the cell reaction and hat is the standard potential of the cell+

,n a competition for electrons, the half$reaction having the higher !more positive"
reduction potential undergoes reduction. The half$reaction ith the loer
reduction potential is therefore forced to undergo oxidation. This means that
here is the first half$reaction given ill occur as reduction and the second ill be
forced to reverse its direction. ,n the cell, the reactions are1
)b#/!s" * 5H
*
!a6" * >#5
/$
!a6" * /e
$
< )b>#5!s" * / H/#
)b!s" * >#5
/$
!a6" < )b>#5!s" * /e
$


Adding the to half$reactions and canceling electrons gives the cell reaction,
)b#/!s" * 5H
*
!a6" * )b!s" * / >#5
/$
!a6" < / )b>#5!s" * / H/#
!This is the reaction that ta%es place in lead storage batteries used to start cars,
motorcycles and boats." The cell potential can be obtained by using 1
(
o
cell @ !standard reduction !standard reduction
potential of the potential of the
substance reduced" substance oxidi8ed"
>ince the first half$reaction occurs as a reduction and the second as an oxidation,
(
o
cell @ (
o
)b#/ (
o
)b>#5
@ 2.EI V !$D.4E V"
@ /.D7 V

ex.2. / )redicting the Cell Reaction and Cell )otential
.hat ould be the cell reaction and the standard cell potential of a galvanic cell
employing the folloing half$reactions+
Al
4*
!a6" * 4e
$
Al!s" (
o
Al
4*
@ 2.EE V
Cu
/*
!a6" * /e
$
Cu!s" (
o
Cu
/*
@ D.45 V
.hich half$cell ould be the anode+
The reaction ith the more positive reduction potential occurs as a reduction3 the
other occurs as an oxidation. ,n this particular half$cell pair, Cu
/*
is reduced and
Al is oxidi8ed.
To obtain the cell reaction, leave the reduction reaction alone and flip the
oxidation reaction.

Cu
/*
!a6" * /e
$
Cu!s"
Al!s" Al
4*
!a6" * 4e
$
The electrons must cancel so multiply so that electrons cancel out. !i.e. cross
multiply the reactions by the electron coefficients", then add the result

4 JCu
/*
!a6" * /e
$
Cu!s"K !reduction"
/ JAl!s" Al
4*
!a6" * 4e
$
K !oxidation"
4 Cu
/*
!a6" * / Al!s" 4 Cu!s" * / Al
4*
!a6"
the anode in the cell is aluminum because that is here oxidation ta%es place. To
obtain the cell potential, e substitute into the cell potential e6uation.
(
o
cell @ (
o
Cu
/*
(
o
Al
4*

@ D.45 V !$2.EE V"
@ /.DD V
;otice that e multiply the half$reaction by factors to ma%e the electrons cancel,
but e do not multiply the reduction potentials by these factors. !Reduction
potentials are intensive 6uantities3 they have the units, volts, hich are ?oules per
coulomb. The same numbers of ?oules are available for each coulomb of charge
regardless of the total number of electrons shon in the e6uation. Therefore,
reduction potentials are never multiples by factors before they are subtracted to
give the cell potential."
)redicting a >pontaneous Reaction
Reduction potentials can also be used to predict the spontaneous reaction
beteen the substances given in to half$reactions, even hen these substances
are not in a galvanic cell. The procedure is very simple because e %no that
the half$reaction having the more positive reduction potential alays undergoes
reduction hile the other is forced to undergo oxidation.
ex.21 .hat spontaneous reaction ill occur if Cl/ and 9r/ are added to a solution
containing Cl
$
and 9r
$
+
There are to possible reduction reactions.
Cl/ * /e
$
< / Cl
$
9r/ * /e
$
< / 9r
$
Refer to a standard reduction potential table.
Cl/ has the more positive potential at 2.4E V. 9r/ has a somehat less positive
potential at 2.DL V. This means the Cl/ ill be reduced and the 9r/ ill be
oxidi8ed. .hen the reaction occurs the half$reactions ill be1

Cl/ * /e
$
< / Cl
$

/ 9r
$
< 9r/ * /e
$
The net reaction ill be Cl/ * / 9r

< 9r/ * / Cl

(xperimentally, e find that chlorine does indeed oxidi8e bromide ion to
bromine, and this fact is used in the synthesis of bromine.
ex./ )redict the reaction that ill occur hen ;i and Ce are added to a solution
that contains both ;i
/*
and Ce
/*
.
;i
/*
has a more positive !less negative" reduction potential than Ce
/*
. Therefore,
;i
/*
ill be reduced and Ce ill be reduced.
;i
/*
!a6" * /e
$
< ;i!s" !reduction"
Ce!s" < Ce
/*
!a6" * /e
$
!oxidation"
;i
/*
!a6" * Ce!s" < ;i!s" Ce
/*
!a6" !net reaction"

Determining .hether a Reaction is >pontaneous
>ince e can predict the spontaneous redox reaction that ill ta%e place among a
mixture of reactants, it should be possible to predict hether or not a particular
reaction ill occur spontaneously as ritten. This can be done by calculating the
cell potential that corresponds to the reaction in 6uestion.
For any functioning galvanic cell, the measured cell potential has a positive
value.
,f e compute the cell potential for a particular reaction based on the ay the
e6uation is ritten and the potential comes out ith a positive value, then the
reaction is spontaneous. ,f the calculated cell potential comes out negative,
hoever, the reaction is nonspontaneous. ,n fact, it really is spontaneous but in
the opposite direction.
ex.2 Determine hether the folloing reactions are spontaneous as ritten. ,f
they are not, give the reaction that is spontaneous.
a" Cu!s" * / H
*
!a6" < Cu
/*
!a6" * H/!g"
b" 4 Cu!s" * / ;#4

!a6" * F H
*
!a6" < 4 Cu
/*
!a6" * / ;#!g" * 5 H/#
>olution
a" the half$cell reactions involved in this reaction are1
Cu!s" < Cu
/*
!a6" * / e
$

/ H
*
!a6" * / e
$
< H/!g"
Crom the ay the reaction is ritten, H
*
is reduced and Cu is oxidi8ed.
Gsing the values from the standard reduction potential table e get
(
o
cell @ (
o
H
*
(
o
Cu
/*

@ !D.DD V" !D.45 V"
@ $D.45 V
The calculated cell potential is negative and therefore the reaction above ill not
be spontaneous in the direction ritten. The spontaneous reaction ill be1
Cu
/*
!a6" * H/!g" < Cu!s" * / H
*
!a6"
b" The half$cell reactions are1
Cu!s" < Cu
/*
!a6" * /e
$

;#4
$
!a6" * 5 H
*
!a6" * 4e
$
< ;#!g" * / H/#
The Cu is oxidi8ed hile the ;#4
$
is reduced.
(
o
cell @ (
o
;#4

(
o
Cu
/*

@ !D.IE V" !D.45 V"
@ D.E/ V
>ince the calculated cell potential is positive, this reaction is spontaneous in the
forard direction.