Silver Electrodeposition from

Sodium and Ammonium

Thiosulfate Solutions

David G. Foster a,b and Jacob Jorné b

aEastman Kodak Company, Rochester, NY 14650
bDepartment of Chemical Engineering,

University of Rochester, Rochester, NY 14727

1
 Silver Recovery from
Photographic Fixer

• Revenue generating
• Environmental compliance
• Removing silver accomplishes two things:
– that which is lost to the effluent is controlled
and minimized
– fixer solution can be recycled and reused

2
 Photographic Fixer
• Removes silver halide from the photographic
emulsion
• Conventionally done by thiosulfate
• Some components regulated by municipalities
– silver
– ammonium (and other) salts
• Plating from ammonium and sodium thiosulfate
solutions necessary

3
 Silver Electrodeposition

• Successfully done for many years

• Majority of information remains empirical

• Solutions evolve to better environmental

positions, silver electrodeposition has
changed
4
Film Processor with Desilvering System
Replenisher
Replenisher

Stabilizer Stabilizer Stabilizer

0:20 0:20 0:20

Bleach Fixer Fixer

0:60 0:60 0:60
Developer
3:15
Electrochemical
Cell
© EASTMAN KODAK Company 1996

5
 Silver Removal from
Photographic Emulsion

In the Photographic Emulsion, silver halide reacts

with thiosulfate:

Ag+ + 2S2O3-2 [Ag(S2O3)2]-3

6
Silver Recovery in Photographic Systems

At the Cathode silver is plated:

[Ag(S2O3)2]-3 + e- Ago + 2S2O3-2

At the Anode sulfite is reduced to sulfate:

SO3-2 + H2O 2H+ + SO4-2 + 2e-

7
 Experimental Setup

• Rotating Stainless Steel disk cathode

– 1 cm in diameter
– incased in Teflon bar 2.5 cm in diameter

• rectangular graphite anode

8
 Effect of Rotation Rate on the Limiting Current for
0.092 M AgBr + 1.0 M (NH4)2S2O3 Solution

70
60
3000 RPM
I/Area (mA/cm )

50
2

40 2000 RPM
1500 RPM
30
1000 RPM
20
500 RPM
10 200 RPM
0
-10
0

100

200

300

400

500

600

700

800

900

1000
-E (mV) vs SCE

9
 Limiting Current vs. Square Root of Angular
Velocity for 0.092 M AgBr + 1.0 M (NH4)2S2O3

60
50
I/Area (mA/cm )
2

40
30
20

10
0
0 5 10 15 20
1/2
Square Root of Angular Velocity (rad/sec)

10
 Effect of Rotation Rate on the Limiting
Current for 1.0 M Na2S2O3 + 0.092 M AgBr

55
I/Area (mA/cm2)

45 3000 RPM
35 2000 RPM
1500 RPM
25
1000 RPM
15 500 RPM
5 200 RPM

-5
0

100

200

300

400

500

600

700

800

900

1000
-E (mV) vs SCE

11
Limiting Current vs Square Root of Angular Velocity
for 0.092 M AgBr + 1.0 M Na2S2O3

60
50
I/Area (mA/cm )
2

40
30
20

10
0
0 5 10 15 20
1/2
Square Root of Angular Velocity (rad/sec)

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 Limiting Current vs
Square Root of Angular Velocity

60
50
I/Area (mA/cm )

0.092 M AgBr + 1.0 M (NH4)2S2O3

2

40
30
20

10
0.092 M AgBr + 1.0 M Na2S2O3
0
0 5 10 15 20
1/2
Square Root of Angular Velocity (rad/sec)

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 Levich Equation

iL = 0.62 n F D2/3 ν-1/6 C0 ω1/2

where:
iL = limiting current density
n = 1 (for silver)
F = Faraday’s Constant
ν = kinematic viscosity
D = diffusion coefficient
ω = angular velocity of rotating disk

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 Walden Product for Sodium and Ammonium
Thiosulfate Systems
SYSTEM VISCOSITY DIFFUSION WALDEN
(g/cm-s) COEFFICIENT PRODUCT
(cm2/s) (cm4/s2)

1 M (NH4)2S2O3 0.0130 4.51 x 10-6 5.86 x 10-8

+0.092 M AgBr

1 M Na2S2O3 0.0147 3.73 x 10-6 5.48 x 10-8

+0.092 M AgBr

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 Current Density vs Potential Curves for Na2S2O3 and (NH4)2S2O3
Solutions with and without AgBr up to -2 V vs SCE

450
1M (NH4)2S2O3 +
400
0.053M AgBr
350
I/Area (mA/cm )
2

300 1M Na2S2O3 +
250 0.053M AgBr
200 1M (NH4)2S2O3
150
100 1M Na2S2O3
50
0
-50
0
200
400
600
800
1000
1200
1400
1600
1800
2000
-E(mV) vs SCE

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 Current Density vs Potential Curves for Na2S2O3 and (NH4)2S2O3
Solutions with and without AgBr up to -2 V vs SCE

150
1M (NH4)2S2O3 +
130 0.053M AgBr
I/Area (mA/cm )

110
2

1M Na2S2O3 +
90 0.053M AgBr
70 1M (NH4)2S2O3
50
1M Na2S2O3
30
10
-10
0
200
400
600
800
1000
1200
1400
1600
1800
2000
-E(mV) vs SCE

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 Standard Potential for Cathodic
Reactions

Ag(S2O3)23- + e- Ag0 + 2S2O32-

-3
EoAg/Ag(S = 0.0164 V
2O3)2

S2O32- + 8H+ + 8e- 2HS- + 3H2O

E0 HS-/S O -2 = 0.221 V
2 3

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 Comparison of Ammonium and
Sodium Thiosulfate Systems
• Limiting Currents for (NH4)2S2O3 system
consistently higher than that for Na2S2O3 system
• Diffusion Coefficient for (NH4)2S2O3 system
greater than that for Na2S2O3 system
• Beginning of a second reaction at -825 mV in the
(NH4)2S2O3 system
• The reduction of thiosulfate is displaced by -400
mV by replacing (NH4)2S2O3 by Na2S2O3

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 Future Work

• Ammonium versus Sodium Thiosulfate

– Advance understanding
– Evaluate the environmental impact
– Effect on industrial silver recovery
• Electrochemistry of sulfur/oxygen
compounds
• Electrochemical side reactions that effect
the photographic emulsion
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 Acknowledgment

We gratefully acknowledge
Eastman Kodak Company
for supporting this work.

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