SUPER IONIC TRANSITION IN AgI AND IMPEDANCE

SPECTROSCOPY
By Rohit Upreti

Objective
To study the Super ionic transition in AgI using impedance spectroscopy.

Theory
Silver Iodide (AgI) is a remarkable compound due to its super-ionic phase
and high Ag+ conductivity. At ambient conditions, AgI occur as a mixture of
Wurzitic-HCP (-phase) and zinc blend-BCC (-phase). This material
undergoes a first order super-ionic transition at 147 C from the AgI in phase to the AgI (-phase) at higher temperature. The -phase exhibits a
highly disordered cation distribution and a rigid crystal framework provided
by the anion sub lattice. The transition between the and forms
represents the melting of the silver (cation) sub lattice. Silver ions move
easily through this structure with low activation energy giving rise to high
ionic conductivity values. In -phase, the cation sub lattice is diffusive while
the anion remains localized in a BCC lattice.

Calculation
Room Temperature = 17.3 C
Conductivity =l/RA where l = 36 mm
A = area of sample = 12.56 mm2
The temperature of sample is given by
T = V/0.04 + Troom
The activation energies for the two phases can be found out from the slope
of the graph using this equation
Ea = Slope x 1.38 x 10^-23 Joule

Observations
Resistance
V
Time
Conductivity
Temperature(Kelvin)
17.18
0.2
0
0.027805995
305.03
16
0.25
61
0.029856688
306.28
16.11
0.3
104
0.029652824
307.53
16.18
0.35
139
0.029524536
308.78
15.53
0.4
170
0.03076027
310.03
15.01
0.45
197
0.031825916
311.28
14.33
0.5
223
0.033336148
312.53
14.11
0.55
248
0.033855918
313.78
13.53
0.6
270
0.035307243
315.03
13.01
0.65
290
0.036718447
316.28
12.43
0.7
311
0.038431778
317.53
11.9
0.75
331
0.040143445
318.78
11.42
0.8
350
0.041830736
320.03
10.52
0.85
370
0.045409411
321.28
10.47
0.9
368
0.045626266
322.53
10.03
0.95
406
0.047627817
323.78
9.55
1
424
0.050021675
325.03
9.18
1.05
441
0.0520378
326.28
8.74
1.1
459
0.054657551
327.53
8.41
1.15
476
0.056802259
328.78
8.03
1.2
492
0.059490286
330.03
7.67
1.25
510
0.062282529
331.28
7.32
1.3
527
0.065260519
332.53
6.97
1.35
544
0.06853759
333.78
6.74
1.4
561
0.070876409
335.03
6.48
1.45
577
0.073720216
336.28
6.23
1.5
595
0.076678491
337.53

5.99
5.78
5.47
5.29
5.12
4.91
4.74
4.11
3.84
3.77
3.76
3.8
4.28
4.48
5.15
5.6
5.9
6.22
6.54
6.8
7.07
7.33
7.57
7.81
7.99
8.11
8.13
8.1
8
7.92
7.79
7.62
7.41
7.15
6.9
6.65
6.4
6.15
5.9
5.67
5.44
5.21
4.99

1.55
1.6
1.65
1.7
1.75
1.8
1.85
1.9
1.95
2
2.05
2.1
2.15
2.2
2.25
2.3
2.35
2.4
2.45
2.5
2.55
2.6
2.65
2.7
2.75
2.8
2.85
2.9
2.95
3
3.05
3.1
3.15
3.2
3.25
3.3
3.35
3.4
3.45
3.5
3.55
3.6
3.65

612
629
647
664
682
702
722
745
770
797
829
872
934
1030
1116
1170
1210
1256
1307
1356
1410
1473
1540
1615
1699
1792
1901
2024
2161
2315
2495
2711
2947
3008
3109
3201
3279
3335
3385
3431
3471
3511
3549

0.079750751
0.08264827
0.087332176
0.090303781
0.093302148
0.097292668
0.100782068
0.116230414
0.124402865
0.126712732
0.127049734
0.125712368
0.111613785
0.106631027
0.092758641
0.085304821
0.080967288
0.076801768
0.073043884
0.070251029
0.067568175
0.065171487
0.063105284
0.061166069
0.05978811
0.058903453
0.058758549
0.058976173
0.059713375
0.06031654
0.061323107
0.062691207
0.064467881
0.066812168
0.069232899
0.071835639
0.074641719
0.077675935
0.080967288
0.084251675
0.087813787
0.091690403
0.095732866

338.78
340.03
341.28
342.53
343.78
345.03
346.28
347.53
348.78
350.03
351.28
352.53
353.78
355.03
356.28
357.53
358.78
360.03
361.28
362.53
363.78
365.03
366.28
367.53
368.78
370.03
371.28
372.53
373.78
375.03
376.28
377.53
378.78
380.03
381.28
382.53
383.78
385.03
386.28
387.53
388.78
390.03
391.28

4.79
4.58
4.39
4.2
4.03
3.96
3.69
3.53
3.38
3.22
3.01
2.94
2.81
2.67
2.55
2.42
2.3
2.18
2.07
1.97
1.87
1.75
1.67
1.58
1.49
1.41
1.33
1.26
1.19
1.12
1.06
0.98
0.87
0.764
0.634
0.449
0.229
0.063
0.011
0.0054
0.0069
0.0056
0.0059

3.7
3.75
3.8
3.85
3.9
3.95
4
4.05
4.1
4.15
4.2
4.25
4.3
4.35
4.4
4.45
4.5
4.55
4.6
4.65
4.7
4.75
4.8
4.85
4.9
4.95
5
5.05
5.1
5.15
5.2
5.25
5.3
5.35
5.4
5.45
5.5
5.55
5.6
5.65
5.7
5.75
5.8

3585
3621
3655
3690
3723
3757
3791
3822
3855
3888
3921
3955
3986
4020
4054
4087
4119
4161
4190
4225
4259
4294
4331
4366
4405
4443
4481
4521
4558
4597
4639
4681
4722
4766
4812
4860
4905
4957
5005
5056
5110
5163
5217

0.099730063
0.104302838
0.108817084
0.113739762
0.118537717
0.120633081
0.129459892
0.135327762
0.141333432
0.148356211
0.158706645
0.162485374
0.170002491
0.178916479
0.187336078
0.197399587
0.207698696
0.219131651
0.230776329
0.242490863
0.255458289
0.272975429
0.286052096
0.302346203
0.320608725
0.338799291
0.359178195
0.37913254
0.401434454
0.426524107
0.450666981
0.487456122
0.549088506
0.625270942
0.753481073
1.063935412
2.086056769
7.582650794
43.42790909
88.46425926
69.23289855
85.30482143
80.96728814

392.53
393.78
395.03
396.28
397.53
398.78
400.03
401.28
402.53
403.78
405.03
406.28
407.53
408.78
410.03
411.28
412.53
413.78
415.03
416.28
417.53
418.78
420.03
421.28
422.53
423.78
425.03
426.28
427.53
428.78
430.03
431.28
432.53
433.78
435.03
436.28
437.53
438.78
440.03
441.28
442.53
443.78
445.03

0.0057

Area(mm2
)
12.56

Graphs

5.85

Length(mm)

5292

l/area
0.4770
6
67

83.80824561

446.28

Results
From the graph the value of activation energies are found to be

Ea1 = 4.988 x 10-20 Joule

Ea2 = 7.8066 x 10-20 Joule
Ea2 Ea1 =( 7.8066 - 4.988) x 10-23 Joule = 2.8186 x 10-20 Joule