Problem Set 4

Po te n t i o me t r y a n d Vo l t amme t r y

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1. A cell was prepared by dipping a Cu wire and a saturated calomel electrode into 0.10 M CuSO4 solution. The Cu wire was
attached to the positive terminal of a potentiometer and the calomel electrode was attached to the negative terminal.
a) Write a half-reaction for the Cu electrode.
b) Write the Nernst equation for the Cu electrode.
c) Calculate the cell voltage.

a) Cu2+ + 2e- ↔ Cu (s) Eo = 0.339 V

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b) Ec = 0.339 - log = 0.309 V
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Saturated calomel electrode E = 0.241 V

a) Ecell = Ec – Ea = 0.309 – 0.241 = 0.068 V

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2. A 10.0-mL solution of 0.050 0 M AgNO3 was titrated with 0.025 0 M NaBr in the cell
S.C.E. || titration solution | Ag(s) Find the cell voltage for 0.1 and 30.0 mL of titrant.

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2. A 10.0-mL solution of 0.050 0 M AgNO3 was titrated with 0.025 0 M NaBr in the cell
S.C.E. || titration solution | Ag(s) Find the cell voltage for 0.1 and 30.0 mL of titrant.

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3. Given: PbI2 (s) ⟷ Pb2+ (aq) + 2I- Ksp = 7.9 x 10-9 Pb2+ + e- ⟷ Pb (s) Eo = -0.126 V
A cell was fabricated consisting of a saturated calomel reference electrode and a lead
indicator electrode that could be used for the measurement of pI. Calculate pI if this cell has
a potential of −0.402 V.

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4. A membrane electrode was developed for the quantitative analysis of penicillin. The
following data were collected using a set of penicillin standards. What is the concentration of
penicillin in a sample that yields a potential of 142 mV?

m = 47.76
b = 331.4

Y = mX + b
E = m log [penicillin] + b
142 mV= 47.76 mV (log [penicillin] ) + 331.4 mV
142-331.4 mV
log [penicillin] = 47.76 mV
[penicillin] = 1.082 x 10-4

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5. A 20.0 g sample of hotdog meat was placed in a blended with 200 mL water and after several minutes
of blending, the solution was filtered, rinsed and diluted to 250.0 mL in a volumetric flask. A combination
sodium-ion/reference electrode placed in the filtrate produced a voltage of 0.090 V. The same
combination electrode in a 4.35 x 10-2 M Na+ standard had a voltage of 0.120 V. Calculate the percentage
of Na+ in the hotdog.
Given: 20.0 g sample 0.250 L Eunk=0.090 [Na ] std = 0.0435 𝐸 = 0.120 𝑉
+

RTF: %Na+

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6. The wastewater from a chemical plant manufacturing sulfuric acid was thought to be contaminated
with lead. A 50.0 mL aliquot of the water was adjusted to pH 5 and a lead indicator and saturated calomel
reference electrode were placed in the solution. The potential difference between the electrodes was -
0.118 V. After the addition of 5.00 mL of a 6.00 x 10-3 M Pb2+ standard, the potential difference was -
0.109 V. Calculate the molar concentration of Pb2+ in the wastewater sample.
Given: 𝐸1 = −0.118 𝑉 𝐸2 = −0.109 𝑉 Cs = 0.0060 M Pb2+ Vs = 5.00 mL RTF: [Pb2+]

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6. The wastewater from a chemical plant manufacturing sulfuric acid was thought to be contaminated
with lead. A 50.0 mL aliquot of the water was adjusted to pH 5 and a lead indicator and saturated calomel
reference electrode were placed in the solution. The potential difference between the electrodes was -
0.118 V. After the addition of 5.00 mL of a 6.00 x 10-3 M Pb2+ standard, the potential difference was -
0.109 V. Calculate the molar concentration of Pb2+ in the wastewater sample.
Given: 𝐸1 = −0.118 𝑉 𝐸2 = −0.109 𝑉 Cs = 0.0060 M Pb2+ Vs = 5.00 mL RTF: [Pb2+]

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Voltammetry
current is measured as the potential is changed as a function of time.

Convection Migration Diffusion

Voltammogram

Measured current
plot of current versus applied potential

limiting diffusion current (Id)

half-wave potential (E ½)
peak current (Ip)
Applied potential
Id = kC
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7. A standard solution contains 3.50 x 10-3 M CdCl2 is excited
by voltammetry and gives a
limited diffusion current at the plateau of 65.3 mA. An unknown water sample that is also
thought to contain cadmium ions is analyzed under identical conditions and gives a limiting
diffusion current of 45.3 mA. What is the concentration of Cd2+ in the sample?
Given: [Cd2+]s = 3.50 x 10-3 Id = 65.3 mA Unknown Cd2+ Id = 45.3 mA RTF: [Cd2+]

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