8

Potentiometry
• Measures the potential at the working electrode for varying concentrations of analyte
without drawing appreciable current.
• Common applications are
1. Measure of pH of consumer products
2. Measure of pH and concentration of pollutants in industrial effluents
3. Measure of CO2 content in oceans
4. Determination of Ka, Kb and Ksp.
5. Potentiometric titrations

• The equipment for potentiometric methods

is simple and inexpensive and includes a RE WE

reference electrode, an indicator electrode/working electrode

and a potential-measuring device. Fig 1

2
 No Absolute Potential

▪ The potential of an electrode is measured relative to the second electrode, which is called
the reference electrode (RE).

▪ The RE for the standard reduction potentials is the standard hydrogen electrode (SHE).

▪ Due to the practical difficulty of using the SHE, 1 atm of flammable H2 gas required and
pH 0 HCl, other REs such as the saturated calomel electrode (SCE) or Ag/saturated AgCl
electrode (SSC) are typically employed.
 Cell diagram

By convention, RE is on left. Eind depends on the

concentration of the analyte
and the electrode is selective
Salt bridge prevents mixing
to the analyte.
of analyte solution with
components of the RE.

Electrolyte in the salt bridge is

usually KCl as mobilities of K+
and Cl- ions are nearly equal
and so Ej ≈ 0 V.
J = junction.
Fig 2

4
 Junction Potentials (Ej)
▪ Small voltage difference (usually several mVs) is found at each end of salt
bridge connecting two half-cells. This occurs due to a charge separation when
two electrolytes with different mobilities are in contact.

Fig 3

Charge separation as chloride ions have greater

mobility than sodium ions thus they diffuse faster.
5
5
 A 0.1 M NaCl solution was placed in
contact with a 0.1M NaNO3 solution.
Which side of the junction is positive?
• Because [Na+] is equal on both sides,
there is no net diffusion of Na+ across
Electrolyte in the salt the junction.
bridge is usually KCl as
mobilities of K+ and Cl- • However, Cl- diffuses into NaNO3 and
ions are nearly equal NO3- diffuses into NaCl.
and so Ej ≈ 0 V.
• The mobility of Cl- is greater than that
of NO3- so the NaCl region will be
depleted of Cl- faster than NaNO3
region that is depleted of NO3-.

• The NaNO3 side will become negative

and NaCl side will become
6
positive
6
 Reference Electrodes
Standard Hydrogen Electrode (SHE) or Normal Hydrogen Electrode (NHE)
Pt/H2(p=1)/H+(a=1, aq)

• The platinum metal, coated with finely divided platinum is

immersed in an aqueous acid solution, which is kept
saturated with hydrogen by bubbling the gas at a constant
pressure over the surface of the electrode.
• The half reaction is

• By convention, the potential of the SHE is assigned a

value of 0.000 V at all temperatures.
Fig 4
• Limitations (1) it is difficult to prepare
(2) inconvenient to use. 7
 Silver / Silver Chloride (SSC) Ag‫׀‬AgCl(sat’d), KCl (sat’d)‫׀׀‬

• Consists of silver electrode immersed in a solution

that is saturated in both KCl and AgCl.

• The half reaction is

• Ag/AgCl electrode has an advantage that they can be

used above 60℃ while calomel electrodes cannot.

• The disadvantage is that silver ions are reactive.

• The potential of saturated Ag/AgCl electrode is +0.199 V at 25 ℃

• Normally prepared with saturated, 1M or 3.5 M KCl. Fig 5

8
Silver / Silver Chloride (SSC) Ag‫׀‬AgCl(sat’d), KCl (1 M)‫׀׀‬

0.059 1
Ag+(aq) + e- → Ag(s) E Ag+ /Ag = EoAg+ /Ag − log
1 [Ag+ ]

[Ag+ ] depends on Ksp of AgCl(s).

K sp = 1.82 × 10−10
−
1 [Cl ]
K sp = [Ag+ ][Cl− ]  =
[Ag+ ] K sp
0.059 [Cl −]
o
EAgCl/Ag = EAg + /Ag − log Fig 6
1 K sp

o 0.059 1 [Cl-] = 1 M, Eo = +0.222 V

EAgCl/Ag = 0.799 − log
1 1.82 × 10−10
o
EAgCl/Ag = 0.222 V 9
10
 Calomel Reference Electrode
• It consists of inner tube containing mercury in contact with a
solution that is saturated with mercury(I) chloride(calomel) and
x M solution of KCl and an outer tube containing a saturated
solution of KCl.
• A small hole connect the two tubes.
• The fritted disk made up of a porous fibre or a piece of porous
Vycor(thirsy glass) helps to contact the analyte solution
• The reaction in this half cell is
• The electrode potential for this half cell depends on the Cl- ion
Fig 7
concentration. Thus the concentration of KCl must be specified.
• The electrode potential of the saturated calomel electrode is
11
0.2444 V at 25 ˚C
 Reference & Working Electrodes

Objective: to measure the

relative amounts of ferrous,
Fe2+ and ferric, Fe3+ ions.

The potential of the left-side

cell is constant, therefore it is
the reference electrode.

Nernst equation
0.199 V
2+
 RT  [Fe ]
Ecell = ER − EL = EFe
o
3+
/Fe 2+
−  ln 3+
− E Ag/AgCl
Fig 8  nF  [Fe ] 12
0.77 V
Which species gives (anode) and which takes (cathode)?

Standard Reduction Potentials (E˚red)

Higher red.
potential, more
easily reduced,
half-cell will be
the cathode.
Strong oxidising
agents.

Lower red. Standard:

potential, more
easily oxidised,
g = 1 atm
half-cell will be the aq = 1 molL-1
anode. a=1
Strong reducing
agents. 13
 0.032 + 0.244

0.231-0.199

0.231

- 0.032 SHE SSC SCE

0.000 0.199 0.244

Fig 9

If an electrode has a potential of -0.231 V with respect to a Ag/sat’d AgCl electrode,

what is the potential with respect to SHE? What is the potential with respect to SCE?
vs. Ag/sat’d AgCl E = -0.231 V

vs. SHE E = -0.231 + 0.199 = -0.032 V

vs. SCE E = -0.244 - 0.032 = -0.276 V
Calculate pIO3 if Ecell = 0.294 V at AgIO3/Ag electrode vs. SCE, given that Eored (Ag+/Ag) = 0.80 V
and Ksp (AgIO3) = 3.1 × 10-8.

Ag+(aq) + e- → Ag(s) [Ag+ ] depends on K sp of AgIO3 (s).

K sp = 3.1 x 10-8
0.059 1
E Ag+ /Ag = EoAg+ /Ag − log −
1 [Ag+ ] + − 1 [IO3 ]
K sp = [Ag ][IO3 ]  =
[Ag+ ] K sp

−
0.059 [IO3 ]
Ecell = E o
Ag+ /Ag
− log − ESCE
1 K sp
−
0.059 [IO3 ]
0.294 = 0.80 − log -8
− 0.244
1 3.1 x 10
−
[IO3 ] = 8.55 x 10-4 M
pIO3 = 3.07

15
 Classification of Indicator Electrodes
• An ideal indicator electrode responds rapidly and reproducibly to the changes in the
concentration of an analyte ion.
• Indicator electrodes are of two types: metallic and membrane
• Metallic indicator electrodes are of 3 types,
1. Electrodes of the first kind,
2. Electrodes of the second kind and
3. Inert redox electrodes.
• Membrane electrodes
- there is no redox process and no current.
- the migration of one type of ion across electrode membrane generates an electric
potential
- membrane electrodes are also called p-ion electrodes.
16
 Electrodes of the first kind
An electrode of the first kind is a pure metal that is in direct equilibrium
with its cation in the solution.
Xn+(aq) + ne- ⇌ X(s)
0.0592 1
Eind = 𝐸𝑋0𝑛+Τ𝑋 – ( )log( )
𝑛 𝑎𝑋𝑛+
0 0.0592
Eind = 𝐸𝑋 𝑛+Τ𝑋 + ( )log(𝑎𝑋 𝑛+ )
𝑛
Ecell = Eind – Eref + Ej
0 0.0592
Ecell = 𝐸𝑋 𝑛+Τ𝑋 + ( ) log(𝑎𝑋 𝑛+ ) – Eref +Ej
𝑛
0.0592
Ecell = K + ( )log(𝑎𝑋 𝑛+ ) ;
𝑛
Fig 10
K = 𝐸𝑋0𝑛+Τ𝑋 – Eref + Ej = constant

17
 Electrodes of the first kind
Not widely used for potentiometric determinations for several reasons.
1. Metallic indicator electrodes are not very selective and respond not only to their own
cations but also other more easily reduced cations.
2. Many metal electrodes, such as zinc and cadmium, can only be used in neutral or
basic solutions because they dissolve in acids.
3. Other metals are so easily oxidized that their use is restricted to solutions that have
been deaerated.
4. Certain harder metals, such as iron, chromium, cobalt, and nickel, do not provide
reproducible potentials.
For all the reasons above, the electrodes of first kind that have been used in potentiometry
are Ag/Ag+ and Hg/Hg22+ in neutral solutions and Cu/Cu2+, Zn/Zn2+, Cd/ Cd2+, Bi/Bi2+, Tl/Tl+
and Pb/Pb2+ in deaerated solutions.
18
 Electrodes of the second kind
• Metals serve as indicator electrode for their own cations and
also respond to the activities of anions that form sparingly
soluble precipitates or stable complexes with metal cations.

• The Nernst expression for this process at 25℃ is

• Eind = E0AgCl/Ag – 0.0592 log aCl- = E0AgCl/Ag + 0.0592 pCl-

• Potential of a silver electrode is proportional to pCl-, the

negative log of the chloride ion activity

Ecell = K - 0.0592 log(𝑎𝐶𝑙− ) ;

K = E0AgCl/Ag – Eref + Ej = constant

Fig 11 19
 Inert metallic electrode for redox systems

• Platinum, gold, palladium, and carbon can be used to monitor redox systems.
• Potential of platinum electrode immersed in a solution containing cerium(III) and
cerium(IV) is
o 0.059 𝑎𝐶𝑒 3+
EInd = ECe4+ /Ce3+ − log
1 𝑎𝐶𝑒 4+

• Hence platinum electrode is a convenient electrode for titrations involving

standard cerium(IV) solutions.

20
 Membrane Indicator electrode

• The potential that appears across a thin glass membrane that separates two
solutions with different hydrogen ion concentrations, determines the pH.
• Further more many other type of membranes that respond selectively to many
other ions, lead to the development of new class of indicator electrodes called ION
SELECTIVE ELECTRODES
• Membrane electrodes are sometimes called p-ion electrodes because the data
obtained from them are usually presented as p-functions, such as pH, pCa, or pNO₃
• A typical glass electrode for measuring pH is discussed in the next slide.

21
 The glass electrode for measuring pH
The cell consists of a glass indicator electrode and a
saturated calomel reference electrode immersed in the
solution of unknown pH.
The indicator electrode consists of a thin, pH-sensitive glass
membrane sealed onto one end of a heavy-walled glass or
plastic tube.
The tube contains a small volume of dil HCl saturated with
AgCl. Ag wire in this solution is Ag/AgCl reference electrode
(internal). Calomel electrode is the external reference
electrode.

Fig 12

22
 The glass electrode

• The concentration difference between the

two sides of the glass membrane, produces
the potential difference that we measure
with a pH meter
• The internal and external electrode are just
the means of making the electrical contact
and their potentials are constant except for
the junction potential.
• The characteristics of the membrane helps
us to understand the mechanism that
produce the membrane potential.
Commonly used combination probe consisting of both
an indicator glass electrode and a silver/silver chloride
reference with a second silver/silver chloride electrode
serving as the internal reference.
23
 Glass membrane
• Corning 015 glass is widely used for membranes
and it consists of approximately 22% Na2O, 6%
CaO and 72% SiO2.
• This composition works for pH up to 9.
• Above pH 9 the glass becomes responsive to
sodium and other singly charged ions. Hence we
replace Na and Ca in the membrane by Ba and Li
Fig 13
• At higher pH, we use membranes replacing Na
(a) Cross-sectional view of a silicate glass structure. In
and Ca by Ba and Li. addition to the three bonds shown, each silicon is bonded to
an additional oxygen atom, either above or below the plane
• Singly charged Na and Li ions can move around of the paper. (Adapted with permission from G. A. Perley,
Anal. Chem., 1949, 21, 395. Copyright 1949 American
in the lattice are responsible for electrical Chemical Society.) (b) model showing three-dimensional
structure of amorphous silica with Na ion incorporated.
conduction within the membrane.
24
 Glass membrane
• The glass membrane must be hygroscopic so that ion exchange reaction between
the single charged cations in the interstices of the glass lattice and hydrogen ion
from the solution occurs.

• Gl- site is the oxygen atom attached to only one silicon atom.
• The membrane should be hydrated for the above exchange reaction to take place
in order to measure pH.
• Non hygroscopic glasses show no pH function.
• Even hygroscopic glasses lose their pH sensitivity after dehydration.
• However the response of the glass electrode is restored by soaking it in water.

25
 Cross section of
glass membrane

Fig 14

Ion-exchange equilibria on the

surfaces of the glass membrane:
H+ replaces Na+ that is bound to Fig 15
the O- of the glass.
26
 Membrane Potentials
• There are four potentials that develop in the glass electrode
• EAg,AgCl and ESCE are the two reference electrode potentials that are constant.
• A third Ej is the net potential across the salt bridge that separates the calomel
electrode from the analyte solution.
• The fourth, is the boundary potential, Eb ,which varies with the pH of the analyte
solution.
• The two reference electrodes provide electrical contacts with the solutions so
that changes in the boundary potential can me measured.

27
 The Boundary Potential
The boundary potential is obtained from two potentials E1 and E2 that develop at the two
surfaces of the glass membrane where one of the surfaces is in contact with the analyte
solution and other surface is in contact with the internal solution.

a1 is the activity of the analyte solution and a2 is that of the internal solution

The boundary potential is then a measure of the hydrogen ion activity of the external
solution (a1).

When identical solutions and reference electrodes are placed on the two sides of a glass
membrane, the boundary potential should in principle be zero. In fact, however, a small
asymmetry potential(Easy) that changes gradually with time is frequently encountered.
28
 The Glass Electrode Potential

Substituting Eb in the above equation

Eind = L + 0.0592 log a1 = L− 0.0592 pH

Where L is the combination of all three constant terms L’ + EAg/AgCl + Easy

This is similar to metallic indicator electrode though the mechanisms of charge

separation that result in these expressions are considerably different.

0.0592
Eind = 𝐸𝑋° 𝑛+Τ𝑋 + log 𝑎𝑋 𝑛+
𝑛
29
 Possible Errors in pH measurement
1. Standards: pH measurements cannot be more accurate
than our standards which are typically ±0.01 pH unit.
2. Junction potential: If the ionic composition of the analyte
solution is different from that of the standard buffer, the
junction potential will change even if the pH of the two
solutions is the same.
3. Junction potential drift: Drift is attributed to the slow
clogging of the electrodes porous plug with AgCl(s).
4. Equilibrium time: This arises if the time required for an
electrode to equilibrate with a solution is not sufficient.
5. Hydration of glass is necessary.
6. Temperature: The pH meter should be calibrated at the Fig 16
same temperature at which the measurement is taken.

30
 The alkaline and acid error
• In basic solutions, glass electrodes respond
to the concentration of both hydrogen ion
and alkali metal ions. This is called alkaline
or sodium error.
• Error = pHread −pHtrue
• In acidic solutions where the pH is less than
about 0.5, the read pH value is higher than
actual value. This is called acid error.
• This is because the glass is saturated with H+
and cannot be further protonated.

Fig 17
The magnitude of the resulting
alkaline/acid error for different glass
membranes is shown here
31
 Glass electrodes for other cations

• Incorporation of Al2O3 or B2O3 in glass compositions, permit the

determination of cations other than hydrogen.

• The glass electrodes are developed for the following cations Na+ K+,
NH4+, Rb+, Cs+, Li+, and Ag+

• Glass electrodes for Na+, Li+, NH4+ and the total concentrations of
univalent cations are available from commercial sources.

32
 Liquid – Membrane Electrodes
• The potential of liquid-membrane electrodes develops across the
interface between the solution containing the analyte and a liquid-ion
exchanger that selectively bonds with the analyte ion.

• Here is the diagram of a liquid-membrane electrode for calcium.

It consists of a conducting membrane that selectively binds
calcium ions, an internal solution containing a fixed concentration
of calcium chloride, and a silver electrode that is coated with
silver chloride to form an internal reference electrode.

• The relationship between the membrane potential and the calcium

ion activities is given by an equation
0.0592 𝑎
Eb = E 1 – E2 = ( ) log ( 1 )
2 𝑎2 Fig 18
where a1 and a2 are the activities of calcium ion in the external
and internal solutions respectively.
33
Since the calcium ion activity of the internal
solution is constant

0.0592 0.0592
Eb = N + ( ) log 𝑎1 = N −( ) pCa
2 2

Where N is a constant. This equation is similar to

Eb = L + 0.0592 log a1 = L- 0.0592 pH Comparison of a liquid-membrane calcium

ion electrode with a glass pH electrode.
Performance of the electrode is independent of pH (Courtesy of Orion Research, Boston, MA.)
in the range of 5.5 to 11. At low pH levels,
hydrogen ions undoubtedly replace some of the Fig 19
calcium ions on the exchanger; the electrode then
becomes sensitive to pH as well as to pCa.

34
35
 Crystalline membrane electrodes
• Membranes prepared from cast pellets of silver halides have been used
successfully in electrodes for the selective determination of Chloride, bromide
and iodide ions
• The membrane for fluoride ion selective electrode consists of a slice of single
crystal of lanthanum fluoride that has been doped with europium(II) fluoride to
improve its conductivity.
• Mixtures of PbS, CdS and CuS with Ag2S provide membranes that are selective
for Pb2+, Cd2+ and Cu2+ respectively.
• The potential that develops across crystalline solid state electrodes is described
by a relationship
For cations For anions
0.0592 0.0592
Ecell = K − ( )pX Ecell = K + ( )pA
𝑛 𝑛
36
Solid state ion selective electrodes

37
 Fluoride ion selective electrode
• A crystalline electrode for fluoride ion is available form
commercial sources.

• The membrane consists of a slice of a single crystal of Fig 20

lanthanum fluoride that has been doped with europium
(II) fluoride to improve its conductivity.

• The membrane supported between a reference solution

and the solution to be measured shows a theoretical
response to changes in the fluoride ion over other
common anions by several orders of magnitude.

• Only hydroxide ion appears to offer serious interference.

Fig 21 38
 Ion – Sensitive Field Effect Transistors (ISFETs)

• The field effect transistor, or the metal oxide field effect transistor
(MOSFET), is a tiny solid state semiconductor device.
• ISFETs offer a number of significant advantages over membrane
electrodes, including ruggedness, small size, inertness toward harsh
environments, rapid response, and low electrical impedance.
• ISFETs do not require hydration before use and can be stored
indefinitely in the dry states.

39
 Gas sensing probes

• Gas sensing probes consist of a tube containing a

reference electrode, a specific ion electrode, and an
electrolyte solution. A thin, replaceable, gas-
permeable membrane attached to one end of the
tube serves as a barrier between the internal and
analyte solutions.
• A microporous membrane is fabricated from a
hydrophobic polymer, highly porous, allows the free
passage of gases and water repellent. Hence prevent
water and solute ions from entering the pores.
Fig 22

40
 Gas sensing probes
• The transfer of CO2 gas to the internal solution is
given by the set of equations.
• The last equilibrium causes the pH of the internal surface
film to change.
• This change is detected by the internal glass/calomel
electrode system.
• The overall process and the cell potential expression are
given below:

Where L is a constant
41
 Equations Governing Direct Potentiometry
Indicator electrode is always treated as the right-hand electrode and the reference
electrode as the left-hand electrode
For direct potentiometric measurements, the potential of a cell can then be expressed in
terms of the potentials developed by the indicator electrode the reference and a junction
potential.

For the cation Xn+ at 25 ˚C, the electrode response takes the general Nernstian form

Where L is a constant and ax is the activity of the cation;

For metallic electrodes L is just the standard electrode potential and for membrane
electrodes L is the summation of several constants
42
Combining the above equations

The constant terms in parentheses can be combined to give a new constant K.

Where K = Ej –Eref + L

For an anion An-, the sign of the equation is reversed

𝐸𝑐𝑒𝑙𝑙 −𝐾 𝑛(𝐸𝑐𝑒𝑙𝑙 −𝐾)
pA = 0.0592 =
0.0592
𝑛

Hence, for cations For anions

0.0592
Ecell = K − ( )pX 0.0592
𝑛 Ecell = K + ( )pA
𝑛
43
 Potentiometric titrations
• A potentiometric titration involves measurement of the potential
of a suitable indicator electrode as a function of titrant volume.
• Potentiometric titrations offer advantages over direct
potentiometry. Because the measurement is based on the titrant
volume that causes a rapid change in potential near the
equivalence point. Potentiometric titrations are not dependent
on measuring absolute values of Ecell .
• Thus the titration is relatively free from junction potential
uncertainties because the junction potential remains
approximately constant during the titration.
• Even the reference electrode potential does not need to be
known accurately in a potentiometric titration.
• The results are obtained in terms of the analyte concentration
Fig 23
even though the electrode responds to activity. Hence, ionic
strength effects are unimportant in the titration procedure. 44
 Titration curve
Detecting the end point
There are several methods that can be used to determine the end
point of a potentiometric titration

The direct plot of potential as a function of reagent

volume gives a titration curve with a steeply rising portion. The First derivative curve
inflection point at the steeply rising portion is estimated visually and
taken as the end point.

The second method is to calculate the change in potential per unit

volume of titrant (dE/dV) and plot it as a function of average volume
V. This plot shows a maximum at the point of inflection.
Second derivative curve

The other method is to plot the second derivative curve that changes
sign at the point of inflection.
However all the three methods have their advantages and
disadvantages. Fig 24
45
Titration of 2.433 mmol
of chloride ion with
0.1000 M silver nitrate.

The spike at 24.3 till 24.4

mL locates the end point
for E Vs SCE

In the first derivative the

maxima is located
between 24.3 and 24.4
mL

In the second derivative

the sign changes between
24.3 and 24.4 mL
46
An Example of a Metallic Electrode
Potentiometric Titration

Use Ag and Calomel electrodes to

measure the conc. of Ag+.

A 50.0 mL solution containing 0.100 M

NaNO3 was titrated with an unknown
concentration of AgNO3. Calculate the
pAg+ at the voltages 0.069, 0.27 and
added 0.48 V.

−
Indicator electrode: Ag+(aq) + e → Ag(s)
Fig 25

47
E = E Ag+ /Ag − ESCE
E = 0.556 - 0.059 pAg+
0.059 1
= EoAg+ /Ag − log +
− ESCE
1 [Ag ] y = c + mx
1
= 0.80 − 0.059 log +
− 0.244
[Ag ] 0.6
1 ∆pAg+ = +1
= 0.556 − 0.059 log 0.5
∆Ag+ = ↓10 fold
[Ag+ ] End
0.4 ∆E = -0.059V
= 0.556 + 0.059 log[Ag+ ]

Eind / V
0.3
Nernstian
+
= 0.556 - 0.059 pAg
0.2
y = -0.059x + 0.556
0.069 = 0.556 − 0.059 pAg+ 0.1 R² = 1
pAg+ = 8.3 Start
0
0 5 10
+
0.27 = 0.556 − 0.059 pAg pAg+

pAg+ = 4.8 [Ag+] can be calculated at

measured voltage.
0.48 = 0.556 − 0.059 pAg+ E α [Ag+]
Fig 26
pAg+ = 1.3 48
Potentiometric Precipitation Titration

Use Ag and Calomel electrodes to

measure the conc. of Cl-.

A 50.0 mL solution containing an

unknown concentration of NaCl was
titrated with 0.100 M AgNO3. Calculate
the pCl- at the voltages 0.069, 0.27
added
and 0.48 V.

Indicator electrode: Ag+(aq) + e- → Ag(s)

Fig 27

49
 0.059 1
E = EoAg+ /Ag − log
1 [Ag+ ]
E = -0.019 + 0.059pCl−
[Ag+ ] depends on K sp of AgCl(s).
K sp = 1.8 x 10-10
−
y = c + mx
1 [Cl ]
K sp = [Ag+ ][Cl− ]  = 0.6
[Ag+ ] K sp y = 0.059x - 0.019
0.5
0.059 [Cl− ] R² = 1.000
E =E o
Ag+ /Ag
− log − ESCE 0.4
End
1 K sp

Eind / V
0.3
0.059 [Cl− ]
= 0.556 − log
1 1.8 x 10-10 0.2 ∆pCl- = +1
∆Cl- = ↓10 fold
= 0.556 − 0.059(log[Cl− ] - log1.8 x 10-10 ) 0.1 ∆E = +0.059V
= 0.556 − 0.059log[Cl− ] + 0.059log1.8 x 10-10 0 Start Nernstian
0 2 4 6 8 10
= -0.019 + 0.059pCl−
pCl-

0.069 V  pCl− = 1.5 [Cl-] can be calculated at

0.27 V  pCl− = 4.9 measured voltage.
E α [Ag+] α 1 / [Cl-]
0.48 V  pCl− = 8.5
50
For the experiment on the previous two slides, what is the potential at equivalence point?
If this potential was reached after 24.4 mL of AgNO3 was added, what is the concentration
of NaCl in the original 50 mL solution?
0.059 1
E = EoAg+ /Ag − log NaCl + AgNO3 → AgCl + NaNO3
1 [Ag+ ]
1: 1 reaction
At equivalenc e point, depends on
dissociation of AgCl (ppt) : 0.1 x 0.0244
c NaCl =
K sp = [Ag+ ][Cl− ] 0.05
= 0.0488 M
K sp = [Ag+ ]2
K sp = [Ag+ ]
First Derivative
Plot
0.059 1
E = EoAg+ /Ag − log − ESCE
1 K sp
0.059 1
= 0.556 − log
1 1.8 x 10-10
= 0.27

51
Which side of the 0.05 M NaCl / 0.05 M LiCl junction will be positive?

Answer LiCl

52