International Journal of Engineering and Technical Research (IJETR)

ISSN: 2321-0869, Volume-2, Issue-11, November 2014

Anodic Corrosion of Copper in Presence of Polymers

A.M. Ahmed, Y.A. Aggour, M.A. Shreadah, Mona Darweesh and Eman Sallam

investigated. The rate of copper corrosion is determined by

Abstract The rates of anodic corrosion of copper plates in measuring the anodic limiting current, i.e. at which polishing
different concentration of phosphoric acid (6, 8, 10, 12 and 14 take place.
mol) were determined by measuring the limiting current of
anodic dissolution. The rates of corrosion were measured in II. EXPERIMENTAL PROCEDURE
absence and in presence of polyethylene glycol 400,
polyethylene glycol 800, polyethylene glycol 4000, polyethylene Materials
glycol 6000 (PEG), polyvinyl alcohol 6000 (PVA) and starch. It Analar grade H3PO4 (98% w/w), supplied by BDH chemicals
is found that, the rate of corrosion depends of type of Ltd, was used for preparation of the electrolyte. Six organic
inhabitations and its concentrations. The rate of corrosion polymers (polyethylene glycol 400, polyethylene glycol 800,
decreases by amount ranging from 9.7 to 80.1 % depending on polyethylene glycol 4000, polyethylene glycol 6000,
organic compounds and its concentrations. Those compounds polyvinyl alcohol 6000 and starch) were used in this work.
verify Langmuir and Flory- Huggins isotherm. Thermodynamic
parameters were given.
Solution Composition
Index Terms Electrodeposition, Corrosion Inhibition,
Blank solution consist of 8 M H3PO4 Different concentrations
Limiting Current, Mass Transfer, Thermodynamic Parameters, from the organic polymers in the range of concentration (10 -5
Polymers. - 10-2 mol / l) were used.
Apparatus and techniques
I. INTRODUCTION Fig. a. represents the cell and the electrical circuit that has
been used in this work. The cell consisted of a rectangular
Due to its excellent electrical and thermal conductivities and
plastic container having the dimensions (5.15.010.0 cm)
good mechanical workability, copper is a material commonly
with electrodes fitting the whole section. Two electrodes,
used in heating and cooling systems. Scales and corrosion
each as rectangular copper plate of 10 cm height and 5 cm
products have negative effect on heat transfer and cause
width, are located 5.1 cm apart. A porous poly vinyl chloride
decrease in the heating efficiency of equipment, which
diaphragm is used to prevent the effect of H2 bubble. The
requires periodic descaling and cleaning in hydrochloric acid
electrical circuit during this work consisted of 6 Volt D.C.
pickling solution
power supply of 6 volt with a voltage regulator and
Most corrosion inhibitors can eliminate the undesirable
multi-range ammeter was connected in series with cell.
destructive effect and prevent metal dissolution. Copper
Potential differences were obtained by increasing the cell
normally does not displace hydrogen from acid solutions and
current stepwise and measuring the steady state anode
therefore, is virtually not attacked in non-oxidizing
potential against a reference electrode which consisted of a
conditions. In fact, if hydrogen bubble is passed through a
copper wire immersed in a cup of Luggin probe filling with
solution of copper salt, it reduces copper as fast as the process
phosphoric acid solution containing organic compound at
occurs [1]. Copper dissolution in acidic medium has been
concentration similar to that in the cell, the tip of Luggin
studied by several researchers [2-7]. Corrosion inhibitors can
probe is placed 0.5 - 1 mm tube from the anode surface. The
be used to prevent copper dissolution. Polymers are found to
Potential difference between the anode and the reference
have excellent inhibition properties in several corrosion
electrode is measured by high impedance potentiometer.
environments [8]. The molecules contain nitrogen atoms and
Ortho-phosphoric acid concentration is prepared from Analar
it usually prevents copper by staining and tarnishing [9].
ortho-phosphoric acid and distilled water. The anode height
is 2 cm. before each run the block part of the anode is
One of the most important methods in the protection of copper
insulated with poly-styrene lacquers and the active surface of
against corrosion is the use of organic polymer inhibitors
the anode is polished with fine emery paper, degreased with
[10]. Organic compounds containing polar groups including
trichloroethylene, Washed with alcohols and finally rinsed in
nitrogen, sulfur, oxygen [11-17] and heterocyclic compounds
distilled water. Electrode treatment is similar to that used by
with polar functional groups and conjugated double bonds
Wilke29. The rate of copper corrosion under different
have been reported to inhibit copper corrosion [18-20]. The
conditions is determined by measuring the limiting Current at
inhibiting action of these organic compounds is usually
25C.
attributed to their interactions with the copper surface via
their adsorption. Polar functional groups are regarded as the
reaction center that stabilizes the adsorption process [21].
In general, the adsorption of an inhibitor on a metal surface
depends on the nature and the surface charge of the metal, the
adsorption mode, its chemical structure and the type of
electrolyte solution. Polymers are known to be very effective
inhibitors for metal and alloys in different corrosion media.
In this study the effect of some polymers on the inhibition of
copper corrosion in 8 M H3PO4 at different condition has been Fig. a. Schematic diagram of the apparatus

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 Anodic Corrosion of Copper In Presence Of Polymers

III. RESULTS AND DISCUSSION M*106 25C 30C 35C 40C 25C 30C 35C 40C

Leveling process 0.0 710 750 800 850 710 750 800 860
Fig. 1- 3 and Table 1 show the polarization curves for the copper 0.5 590 610 630 650 510 530 550 570
electrode in 8 M H3PO4 solutions in presence of different
concentrations of polyethylene glycol 400 and starch, respectively, 1.0 550 470 580 600 480 495 510 530

using divided cell at 25C. 1.5 510 525 540 550 420 435 450 470
The limiting current at which polishing take place was
2.0 470 480 490 500 370 385 400 420
determined from those polarization curves and used to
calculate the mass transfer coefficient (K) of copper polishing 2.5 450 460 470 480 300 320 340 350
in H3PO4 from the equation: 3.0 400 410 420 440 240 260 280 300
(1)
K= I / zFCo 5.0 350 370 385 400 145 160 180 200

where,
I: limiting current, mA.
F: Faraday constant. 0.5 M * 10-4 1.0 M* 10-4 1.5 M* 10-4 2.0 M* 10-4

Co: concentration of saturated copper phosphate. 2.5 M* 10-4 3.0 M* 10-4 5.0 M* 10-4

z: valency.
800

The values of the limiting current for all compounds at

different temperatures are given in Table1. Leveling is the 700

principle process in electropolishing [22].

Mayer explained the necessity to separate between anode and 600

cathode by non-conductive slit to prevent the gas bubbles

transfer to the anode surface and to enhance the homogenous 500
I (mA)

distribution of electric current [23]. The study of leveling is

based on the classical current voltage curves of 400

electropolishing as shown in Figs. 1-3 typical polarogram

obtained in this study for polymers in case of divided cell. 300

Table 1. The values of limiting current (mA) at different 200

temperatures for all compounds used in case of divided cell.
100
Conc. Polyethylene glycol 400 Polyethylene glycol 6000 90 290 490 690 890 1090 1290

6 V (mV)
M*10 25C 30C 35C 40C 25C 30C 35C 40C

0.0 710 750 800 860 710 750 800 860

Fig. 1. The relation between I (mA) and V (mV) in presence
of polyethylene glycol 400 at 25C and 8 M H3PO4 for
0.5 650 670 720 730 570 585 600 620 divided cell at 1 cm height.
1.0 580 600 630 640 540 540 555 570

1.5 550 570 590 610 490 510 530 545

0.0 M *10^-4 0.5 M *10^-4 1.5 M *10^-4
2.0 510 530 540 550 460 480 500 520

2.5 470 485 500 530 420 435 450 470

2.5 M *10^-4 5.0 M * 10^-4
3.0 430 445 460 500 390 405 420 430

5.0 405 420 435 450 275 290 310 330 1000
Conc. Polyethylene glycol 800 Polyvinyl alcohol 6000 800
I (mA)

M*10 6
25C 30C 35C 40C 25C 30C 35C 40C 600
0.0 710 750 800 860 710 750 800 860
400
0.5 620 640 660 680 550 570 585 600
200
1.0 565 585 600 620 520 540 555 570

1.5 530 545 560 580 490 500 510 520

0
2.0 485 500 515 570 430 445 450 465 0 200 400 600 800 1000 1200 1400
2.5 460 470 480 490 410 425 440 450
V (mV)
3.0 425 440 455 470 370 380 390 405

5.0 385 400 410 420 210 230 250 280

Fig. 2. The relation between I (mA) and V (mV) in presence
Conc. Polyethylene glycol 4000 Starch of polyethylene glycol 800 at 25C and 8 M H3PO4 for
divided cell at 1 cm height.

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 International Journal of Engineering and Technical Research (IJETR)
ISSN: 2321-0869, Volume-2, Issue-11, November 2014
The above equation is based on the finding of previous studies
0.0 M *10^-4 0.5 M *10^-4 1.5 M *10^-4 [25].
2.5 M *10^-4 5.0 M * 10^-4
The percentage of inhibition, % IE, can be calculated from the
following equation:
1000
(3)
800 % IE = I-Il/I 100
I (mA)

600
where :
400
200 I and I1 are the limiting current densities in absence and presence of
0 the organic compounds
0 200 400 600 800 1000 1200 1400
Fig. 4. and Table 2 show that the percent inhibition caused by
V (mV) organic compounds ranges from 9.7% to 80.1% depending on
the organic compounds and their concentration.
Fig. 3. The relation between I (mA) and V (mV) in presence
The limiting current decreases with increasing the
of polyethylene glycol 4000 at 25C and 8 M H3PO4 for
concentration of polymers which agrees with the findings of
divided cell at 1 cm height.
other authors who worked within the same range of
concentration using other inhibitors [26].
Effect of organic compounds concentration on the
limiting current
The decrease in the limiting current with increasing the
The rate of electropolishing which is represented by the concentration of organic compounds is attributed to:
anodic limiting current decreases with increasing the
(a) The solubility of dissolved copper phosphate in ortho
concentration of organic additives as shown in Table 2. It is
phosphoric acid, which is responsible for the limiting
recommended, on the basis of results, that it may use in this
current, decreases with increasing organic compound
range of concentration to inhibit the corrosion of copper metal
concentration.
in 8 M H3PO4 acid in presence of organic compounds to be
used in this work [24]. (b) The viscosity of the solution increases with increasing
polymers concentration with consequence decrease in
The mass transfer coefficient of polishing process, which is
the diffusivity of' Cu2+ according to Stokes-Einstein
used in data correlation, is calculated from the limiting current
equation [27].
using the equation:
K= I / zFACs (2)
Table 2. The relation between percentage inhibition and concentration of all compounds at 25C.
% Inhibition
C x 105
Polyethylene Polyethylene Polyethylene Polyethylene Polyvinyl
mol.l-1 Starch
glycol 400 glycol 800 glycol 4000 glycol 6000 alcohol 6000
0.5 9.7 13.9 18.1 20.8 23.6 29.2
1.0 19.4 21.5 23.6 25.0 27.8 33.3
1.5 23.1 26.4 29.2 31.9 40.3 48.6
2.0 29.2 32.6 34.7 36.1 40.3 48.6
2.5 34.7 36.1 37.5 41.7 43.1 58.3
3.0 40.2 40.9 41.7 45.8 48 66.7
5.0 43.8 46.5 51.4 61.8 70.8 80.1

Compound I Compound II Compound III Compound IV Compound V Compound VI

89

79

69
% inhibition

59

49

39

29

19

9
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5
C * 10^5

Fig.4. The relation between % inhibition and concentration of all compounds at 25C.

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 Anodic Corrosion of Copper In Presence Of Polymers

Adsorption Isotherm surface coverage with concentration variation for divided

The values of I obtained at different temperatures permits the cell.
calculation of activation energy Ea according to Arrhenius From above, it is concluded that all compounds verify
equation: Langmuir Isotherm show in Figs. 5 to 10.
Figs.11 to 16 shows the Flory-Huggins adsorption isotherm
(4) for electropolishing in H3PO4 plotted as log /C against log
log I = -Ea/2.303 RT + log A (1- ) at 25C. A straight line is obtained with a slope x and
intercept log xK.
The plot of log I against 1/T gave a straight line where A is The experimental data fit the Flory-Huggins adsorption
pre-exponential factors R the gas constant and T is absolute isotherm which is represented by:
temperature. log /C = log xK + xlog (1- ) (7)
The slope of the straight line is proportional to Ea. the where x is the number of water molecules replaced by one
activation energy of process is an important parameters to molecule of the inhibitor. It is clear that the surface coverage
determining the rate controlled step. If the rate controlling data are useful for discussing adsorption characteristics.
step is diffusion of species in boundary layer Ea is generally The adsorption of inhibitors at metal/solution interface may
28 kj/mole while Ea usually > 43 kj/mole when reaction is be due to the formation of either electrostatic or covalent
chemically controlled. bonding between the adsorbents and the metal surface atoms
Table 6 and 7 shows that the values of Ea are lower than 43.3 [29].
kj/mole characterizing diffusion process to controlling The kinetic adsorption isotherm may be written in the form:
electroplating process.
(8)
log /1- =log k'+ y log C

where y is the number of inhibitor molecules occupy one

Application of Langmuir isotherm active site. The binding constant of adsorption K= k'1/y , where
1/y is the number of the surface active sites occupied by one
Inhibitor adsorption characteristics can be estimated by using molecule of the inhibitor, and k is the binding constant.
the Langmuir isotherm given by the following equation [28]:
Figs. 17 to 22 show the relation between log /1- and log C
(5) at 25C, and the calculated values of 1/y and K are given in
KC = /1- Table 4.

The values of 1/y depend on the type of polymers derivatives.

= Ib I/ Ib (6)
From Table 4 it is obvious that the value of 1/y for polymers
derivatives is approximately one suggesting that the
where:
compound attached to one active site per inhibitor molecule.
: is the part of surface covered with adsorbed organic
compound. For other inhibitors, the values of 1/y are higher than one,
C : is the concentration of organic compound, mol.cm-3. indicating that, the given inhibitors molecules attached to
I : is the limiting current in presence of organic more than one active site. The free energy of adsorption
compound. (Gads) at different concentration is calculated from the
Ib : is the limiting current in absence of organic following equation:
compound.
K : is the Langmuir constant. (9)
Gads = - RTIn (55.5K)
Plot of / (1- ) against C should yield a straight line. Table 3
gives the data of , / (1- ) and C for all polymers and the

Table 3. The data for adsorption isotherm of copper at 25 C for different polymers
Conc.
% Inh. log C /1- log( /1- ) 1- log(1- ) log /C
M*104
Polyethylene glycol 400
0.5 9.72 -4.30 0.097 0.108 -0.97 0.92 -0.04 3.29
1.0 19.44 -4.00 0.194 0.241 -0.62 0.81 -0.09 3.28
1.5 23.61 -3.82 0.236 0.309 -0.51 0.76 -0.12 3.20
2.0 29.17 -3.70 0.292 0.412 -0.39 0.71 -0.15 3.16
2.5 34.72 -3.60 0.347 0.532 -0.27 0.65 -0.19 3.14
3.0 40.28 -3.52 0.402 0.674 -0.17 0.60 -0.22 3.13
5.0 43.75 -3.30 0.438 0.778 -0.11 0.56 -0.25 2.94
Polyethylene glycol 800
0.5 13.89 -4.30 0.139 0.161 -0.79 0.85 -0.07 3.44
1.0 21.53 -4.00 0.215 0.274 -0.56 0.78 -0.11 3.33
1.5 26.39 -3.80 0.264 0.358 -0.45 0.74 -0.13 3.25
2.0 32.64 -3.70 0.326 0.485 -0.315 0.68 -0.17 3.21

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 International Journal of Engineering and Technical Research (IJETR)
ISSN: 2321-0869, Volume-2, Issue-11, November 2014
2.5 36.11 -3.60 0.361 0.565 -0.25 0.65 -0.19 3.16
3.0 40.97 -3.52 0.409 0.694 -0.16 0.60 -0.22 3.13
5.0 46.53 -3.30 0.465 0.870 -0.06 0.54 -0.27 2.97
Polyethylene glycol 4000
0.5 9.72 -4.30 0.097 0.108 -0.97 0.92 -0.04 3.29
1.0 19.44 -4.00 0.194 0.241 -0.62 0.81 -0.09 3.28
1.5 23.61 -3.82 0.236 0.309 -0.51 0.76 -0.12 3.20
2.0 29.17 -3.70 0.292 0.412 -0.39 0.71 -0.15 3.16
2.5 34.72 -3.60 0.347 0.532 -0.27 0.65 -0.19 3.14
3.0 40.28 -3.52 0.402 0.674 -0.17 0.60 -0.22 3.13
5.0 43.75 -3.30 0.438 0.778 -0.11 0.56 -0.25 2.94
Polyethylene glycol 6000
0.5 13.89 -4.30 0.139 0.161 -0.79 0.85 -0.07 3.44
1.0 21.53 -4.00 0.215 0.274 -0.56 0.78 -0.11 3.33
1.5 26.39 -3.80 0.264 0.358 -0.45 0.74 -0.13 3.25
2.0 32.64 -3.70 0.326 0.485 -0.315 0.68 -0.17 3.21
2.5 36.11 -3.60 0.361 0.565 -0.25 0.65 -0.19 3.16
3.0 40.97 -3.52 0.409 0.694 -0.16 0.60 -0.22 3.13
5.0 46.53 -3.30 0.465 0.870 -0.06 0.54 -0.27 2.97
Polyvinyl alcohol 6000

0.5 9.72 -4.30 0.097 0.108 -0.97 0.92 -0.04 3.29

1.0 19.44 -4.00 0.194 0.241 -0.62 0.81 -0.09 3.28
1.5 23.61 -3.82 0.236 0.309 -0.51 0.76 -0.12 3.20
2.0 29.17 -3.70 0.292 0.412 -0.39 0.71 -0.15 3.16
2.5 34.72 -3.60 0.347 0.532 -0.27 0.65 -0.19 3.14
3.0 40.28 -3.52 0.402 0.674 -0.17 0.60 -0.22 3.13
5.0 43.75 -3.30 0.438 0.778 -0.11 0.56 -0.25 2.94

Starch

0.5 13.89 -4.30 0.139 0.161 -0.79 0.85 -0.07 3.44

1.0 21.53 -4.00 0.215 0.274 -0.56 0.78 -0.11 3.33
1.5 26.39 -3.80 0.264 0.358 -0.45 0.74 -0.13 3.25
2.0 32.64 -3.70 0.326 0.485 -0.315 0.68 -0.17 3.21
2.5 36.11 -3.60 0.361 0.565 -0.25 0.65 -0.19 3.16
3.0 40.97 -3.52 0.409 0.694 -0.16 0.60 -0.22 3.13
5.0 46.53 -3.30 0.465 0.870 -0.06 0.54 -0.27 2.97

Fig. 5. Langmuir adsorption isotherm for polyethylene glycol Fig. 6. Langmuir adsorption isotherm for polyethylene glycol
400. 800.

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 Anodic Corrosion of Copper In Presence Of Polymers

Fig. 7. Langmuir adsorption isotherm for polyethylene glycol Fig. 11. Flory-Huggins adsorption isotherm at 25C for
4000. polyethylene glycol 400 .

Fig. 8. Langmuir adsorption isotherm for polyethylene glycol Fig. 12. Flory-Huggins adsorption isotherm at 25C for
6000. polyethylene glycol 800 .

Fig. 9. Langmuir adsorption isotherm for polyvinyl alcohol

6000. Fig. 13. Flory-Huggins adsorption isotherm at 25C for
polyethylene glycol 4000.

Fig. 10. Langmuir adsorption isotherm for starch.

Fig. 14. Flory-Huggins adsorption isotherm at 25C for
polyethylene glycol 6000.

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 International Journal of Engineering and Technical Research (IJETR)
ISSN: 2321-0869, Volume-2, Issue-11, November 2014
1.4
y = 0.7958x - 0.2644
1.2
R2 = 0.8454
1

1 + log(/1-)
0.8

0.6

0.4

0.2

0
0.7 0.9 1.1 1.3 1.5 1.7 1.9

5 + log C

Fig. 19. Kinetic adsorption isotherm for polyethylene glycol

Fig. 15. Flory-Huggins adsorption isotherm at 25C for
4000 at 25C.
polyvinyl alcohol 6000. 1.4
y = 0.781x - 0.213
1.2
R2 = 0.9426
1

1 + log(/1-)
0.8

0.6

0.4

0.2

0
0.7 0.9 1.1 1.3 1.5 1.7 1.9

5 + log C

Fig. 20. Kinetic adsorption isotherm for polyethylene glycol

Fig. 16. Flory-Huggins adsorption isotherm at 25C for
6000 at 25C.
starch. 1.6
1.2
1.4 y = 0.8425x - 0.2129
1 y = 0.8918x - 0.5503 R2 = 0.8862
1.2
R2 = 0.9737
1 + log(/1-)
1 + log(/1-)

0.8 1

0.6 0.8

0.6
0.4
0.4
0.2
0.2
0
0
0.7 0.9 1.1 1.3 1.5 1.7 1.9
0.7 0.9 1.1 1.3 1.5 1.7 1.9
5 + log C
5 + log C
Fig. 17. Kinetic adsorption isotherm for polyethylene glycol
400 at 25C. Fig. 21. Kinetic adsorption isotherm for polyvinyl alcohol
6000 at 25C.
1.2
1.8
1 y = 0.758x - 0.3201 y = 1.0222x - 0.2506
1.6
R2 = 0.9886 R2 = 0.9134
0.8 1.4
1 + log(/1-)

1.2
1 + log(/1-)

0.6
1
0.4 0.8

0.2 0.6
0.4
0
0.2
0.7 0.9 1.1 1.3 1.5 1.7 1.9
0
5 + log C
0.7 0.9 1.1 1.3 1.5 1.7 1.9
Fig. 18. Kinetic adsorption isotherm for polyethylene glycol 5 + log C
800 at 25C.
Fig. 22. Kinetic adsorption isotherm for starch at 25C.

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 Anodic Corrosion of Copper In Presence Of Polymers

The value 55.5 is the concentration of water in the solution It is observed that the electropolishing rate increases with rise
mol/1. The values of Gads are giving in Table 5. in temperature for different concentrations of organic
compounds, because adsorption of polymers on copper anode
In all cases, the Gads values are negative and lie in the rank of decreases by increasing temperature.
5.37 - 31.31 k.J/mol. The most efficient inhibitor shows the
most negative value. This suggests that they are strongly Thermodynamic treatment of the results
adsorbed on the metal surface. The negative values of Gads From the integrated form of the Arrhenius equation:
indicate the spontaneous adsorption of the inhibitor. It is ln I = - Ea/RT + ln A (10)
found that the Gads values are more positive than - 40 k.J/mol where R is the gas constant (8.314 kJmol-1), Ea is the
indicating that the inhibitors are physically adsorbed on the activation energy and A is the frequency factor it can be seen
metal surface. Similar results also have been reported [30]. that the gradient is given by Ea/R and the intercept by ln A.
Tables 6 and 7 gave the values of Ea for the compounds used.
Table 4. The values of k, x and 1/y of phosphoric acid in The values for enthalpy of activation H*, entropy of
presence of different organic polymers to Langmuir, activation S*, and free energy of activation G* can also be
Flory-Huggins and Kinetic adsorption isotherm. obtained by using the following equations and are given in
Tables 6 and 7.
Kinetic adsorption Langmuir
Flory-Huggins
Compounds isotherm H* = Ea RT (11)
X K Y 1/y K K S* / R = ln A ln (kTe/h) (12)
Polyethylene 0.154 G* = H* - T S* (13)
1.4396 1669.39 0.8918 1.12 810.59
glycol 400 where:
Polyethylene 0.161
k : is Boltzmann's constant.
2.1706 1721.95 0.7572 1.32 294.04
glycol 800 e : = 2.7183.
Polyethylene 0.187
glycol 4000
1.8727 2027.83 0.6903 1.45 188.93 h : is Plank's constant.
Polyethylene 0.282
1.4195 2913.83 0.7810 1.28 491.81 A : is Arrhenius constant.
glycol 6000
Polyvinyl 0.462 T : is absolute temperature, K.
2.3713 2980.67 0.8425 1.19 997.01
alcohol 6000
R : is the universal gas constant=8.314Jmol-1K-1.
0.833
Starch 0.6374 2682.53 0.9858 1.01 5640.09

Table 5. The values of free energy of adsorption (kJ. mol-1) of The adsorption is usually followed by liberation of heat of
phosphoric acid in presence of different organic polymers adsorption, so that Ea< 0, consequently the rate of adsorption
using different methods. decreases with rise in temperature and as a result, the surface
coverage at given concentration decreases with raising
-Gads temperature.
It is known that an increase in the heat of adsorption leads to
Kinetic Langmuir an increase in the energy of adsorption. However, rising of the
Compounds
Flory-Huggins adsorption temperature acts in the reverse direction, increasing the
isotherm kinetic energy of the molecules, facilitating disruption
(consequently in the physical adsorption).
Polyethylen 5.375
28.35 26.56 In absence of organic substance, the results fit a straight line
e glycol 400
with an activation energy equals to 31.935 k.J.mol-1 which is
Polyethylen 5.470 higher than the values obtained when organic substance was
28.42 24.04
e glycol 800 used as inhibitor.
Polyethylen 5.810
Thus, the low values of activation energy show that:
e glycol 28.83 22.95
4000 [1] The rate of electropolishing of copper from phosphoric
Polyethylen 6.870 acid decreases by adding small amounts of the organic
e glycol 29.73 25.32 substances [31] at temperature above 25C.
6000
[2] The adsorption process is physical adsorption and the
Polyvinyl 8.100 molecules of organic substance are disrupted at
29.78 27.07
alcohol 6000 temperature above 30C completely.
Starch 29.52 31.36 9.600
Tables 6 and 7 show that the entropy S* possess height
negative values indicating a highly ordered organic species
Effect of temperature in the solution under investigation. These values found to be
The effect of temperature on the Cu electropolishing rate in independent on the type of polymers.
absence and presence of polymers was determined in the
temperature range 25, 30, 35, 40C as illustrated in Table 1.

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 International Journal of Engineering and Technical Research (IJETR)
ISSN: 2321-0869, Volume-2, Issue-11, November 2014
Table 6. The values of activation energy and thermodynamic parameters for polyethylene glycol 400 to polyethylene glycol
4000.

Thermodynamic Parameters
Organic C x 105
substances mol.l-1 Ea H* G* - S*
(kJ.mol-1) (kJ.mol-1) (kJ.mol-1) (J.mol-1 k-1)
0.5 5.358 0.003 2.88 0.003 5.74 0.006 182 10
1.0 8.538 0.002 3.17 0.006 57.5 0.012 182 2.1
Polyethylene 1.5 7.240 0.288 4.77 0.023 57.8 0.57 177 0.9
glycol 400 2.0 6.780 0.023 4.30 0.0023 57.9 0.075 180 7.8
3.0 9.033 0.002 7.78 0.0042 58.4 0.084 178 14
5.0 18.460 0.501 16.00 0.501 59.75 0.991 141.8 1.64
0.5 4.78 0.034 2.303 0.034 57.1 0.006 183.7 1.1
1.0 4.85 0.023 2.37 0.023 53.3 0.46 184 7.6
Polyethylene 1.5 9.521 0.04 3.13 0.04 57.17 0.9 211 15.5
glycol 800 2.0 5.61 0.272 3.13 0.21 57.17 0.518 180 8.5
3.0 10.92 2.9 8.44 2.9 58.1 0.55 166 9.5
5.0 6.67 0.299 4.164 0.299 58.2 0.591 181 9.6
0.5 9.2 0.023 6.71 0.23 57.36 4.6 176 7.6
1.0 6.62 0.02 6.141 0.02 58.38 0.04 178.5 6.8
Polyethylene 1.5 5.71 0.008 3.281 0.08 57.6 0.017 182 2.8
glycol 4000 2.0 7.93 0.09 5.45 0.09 57.9 0.032 181 2.8
3.0 7.41 0.95 4.93 0.033 58.3 0.07 179 11.1
5.0 9.78 0.98 7.3 0.98 59 3.5 173 5.6

Table 7. The values of activation energy and thermodynamic parameters for polyethylene glycol 6000 to starch.

Thermodynamic Parameters
Organic C x 105
substances mol.l-1 Ea H* G* - S*
(kJ.mol-1) (kJ.mol-1) (kJ.mol-1) (J.mol-1 k-1)
0.5 8.88 0.048 4.083 0.048 57.574 0.925 179 1.53
1.0 6.10 0.013 3.621 0.013 57.71 0.026 181.4 4
Polyethylene 1.5 1.621 0.02 0.857 0.02 57.86 5.8 196.9 9
glycol 6000 2.0 8.85 0.741 6.371 0.741 58.86 5.1 162 14
3.0 11.554 0.152 9.08 0.152 59.43 0.30 168 4.9
5.0 14.67 0.81 12.196 0.8 59.7 2.7 159 4.6
0.5 4.58 0.006 2.1 0.006 57 0.013 184 2.1
1.0 5.1 0.044 2.621 0.044 57.2 0.0087 183.2 1.4
Polyvinyl 1.5 5.36 0.003 2.88 0.003 57.4 0.006 183.0 10
alcohol 6000 2.0 5.76 0.008 3.28 0.008 57.6 0.0017 182.0 2.8
3.0 11.16 0.21 8.68 0.21 57.8 0.57 164.8 9.55
5.0 6.65 0.3 4.17 0.3 58.2 0.59 181 9
0.5 5.915 0.416 2.98 0.0416 57.278 0.90 182.6 1.5
1.0 5.459 0.006 2.98 0.006 57.42 0.013 182.6 2.15
1.5 6.96 0.247 4.482 0.0247 57.66 0.541 178.3 0.89
Starch
2.0 6.347 0.016 4.483 0.016 57.821 0.032 181 5.39
3.0 7.411 0.035 4.932 0.035 58.2 0.115 178.7 0.11
5.0 9.778 1.77 7.299 1.77 59.063 3.513 5.8

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