International Journal of Polymer Science
Volume 2019 (2019), Article ID 5623873, 11 pages
https://doi.org/10.1155/2019/5623873

Research Article

Investigation of the Specific Retention Volume of the Probe Volume and the Effects on the Polymer-Probe System by Inverse Gas Chromatography

Mustafa Hamdi Karagöz

Department of Chemistry, Van Yüzüncü Yıl University, 65080 Van, Turkey

Correspondence should be addressed to Mustafa Hamdi Karagöz; mhkaragoz@yahoo.com.tr

Received 28 November 2018; Revised 12 March 2019; Accepted 16 April 2019; Published 21 May 2019

Academic Editor: Cornelia Vasile

Copyright © 2019 Mustafa Hamdi Karagöz. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract.

In this study, the effects of probe quantities on retention volume and the physical and thermodynamic results of polymer-probe systems were investigated. For this purpose, by using inverse gas chromatographic method. Alcohols and alkanes with different chemical and physical properties were injected as probes on homopolymer (2-cyclohexylidene-1,3-dioxolane-4-yl-methyl methacrylate) (CHMMA). Probe quantities of 0.3, 0.6, and 0.9 μl were selected, and an injection was made at every 10°C between 40 and 150°C. In addition, 3 μl volume probes were tried but reproducible results were not obtained in these volumes and the detector was observed to be out of order after several injections. It has been observed that the specific retention volume of alcohols and alkanes partially increased by increasing the injection amount. A linear relationship was observed between probe quantities and specific retention volume. This linear relationship is apparent from the specific retention volume values, where the probes are independent of the physical and chemical structures. It was observed that the results obtained in all three injections were close to each other and within acceptable limits. The glass transition temperature of the polymer was determined to be a of 60°C. The thermodynamic data calculated for the injection of different amounts of probes were close to each other.

1. Introduction

The inverse gas chromatography (IGC) is a widely used method for studying the physicochemical and surface properties of polymer-solvent systems of polymers. The method is simple, economical, fast, and accurate.

The IGC method developed by Smidsrod and Guillet was used successfully to determine the physicochemical and surface properties of polymeric materials [1]. Many parameters such as glass transition temperatures, adsorption heats, the weight fraction activity coefficients, free energies, enthalpies of mixing, solubility parameters, interaction parameter, diffusion coefficient, and surface properties of the polymers can be calculated with this method [2, 3]. Vinyl polymers containing the 1,3-dioxane group in their structure have many properties such as negative electron beam, good resistance to dry etching, and herbicide function [4]. Properties of poly (acetyl benzofuran methyl methacrylate) and copolymers made by acrylonitrile are investigated by inverse gas chromatography. The properties of these structurally similar polymers were successfully determined by inverse gas chromatography [5]. The solubility and surface thermodynamics of the polypyrrole chloride were investigated by inverse gas chromatography, and some probes interacted with the polymer but all probes did not dissolve the polymer [6].

In this study, physicochemical properties of poly(2-cyclohexylidene-1,3-dioxolane-4-yl-methyl methacrylate) (CHMMA) were investigated by inverse gas chromatography. In addition, the effect of the probe quantity on the retention volume and polymer-probe system was investigated. The basis of the method is to find out the retention time of the probe injected into the column as a function of time, after the polymers to be examined have been coated with a supporting sheath.

2. Materials and Methods

The probe specific retention volumes, , are calculated from the standard chromatographic relation [7]:

where is the retention times of the probe, is the flow rate of the carrier gas measured at room temperature, is the mass of the polymeric stationary phase, is the column temperature, and and are inlet and outlet pressures, respectively.

The molar heat (enthalpy) () and the molar free energy () of sorption of the probe absorbed by the polymer are given by the following equation [8]:

By incorporating equation (2), we calculated the entropy of sorption of solutes as follows:

where is the probe specific retention volume, is the column temperature (K), is the molecular weight of the probe, and is the gas constant. The adsorption enthalpy of probes adsorbed by the polymer, , is given by the following equation [9]:

Partial molar free energy of mixing (cal/mol) and partial molar entalphy (cal/mol) at infinite dilution are calculated according to the following equations [10]:

The weight fraction activity coefficient, , of the solute probe at infinite dilution is calculated according to the following equation [11]:

The polymer-solute interaction parameter , at infinite dilution of different solutes used in this work, is defined by the following equation:

where is the gas constant, is the specific volume of the polymer, is the molar volume of the solute, is the vapor pressure, and is the second virial coefficient of the solute in the gaseous state. , , and were calculated at the column temperature.

Second virial coefficients, , were computed using the following equation [12]:

where and are the critical molar volume and the critical temperature of the solute, respectively, and is the number of carbon atoms in the solute.

The solubility parameters of polymers, , can be determined by using the following relation:

If the left-hand side of this equation is plotted against , then a straight line with a slope of () and an intercept of is obtained. Solubility parameters of the polymer, , can be calculated from both the slope and intercept of the straight line [13].

Ethyl alcohol, 1-propyl alcohol, 1-butyl alcohol, 1-pentyl alcohol, n-hexane, n-heptane, n-octane, and n-nonane were used as probes in chromatographic purity from the Merck & Company. Chromosorb W (80-100 Mesh) from the Polymer SIĞMA Company was coated 10% by weight on the polymer. The coated polymer weight is 0.228 grams. The 2-cyclohexylidene-1,3-dioxolane-4-yl-methyl methacrylate (CHMMA) polymer used in the experiment was synthesized for the first time in the laboratory of the Department of Chemistry of Fırat University [14]. GC-2010 model Shimadzu brand gas chromatography was performed by adding apparatus suitable for filled column analysis. This column is a polymer steel barrel with a diameter of 3.2 mm and a length of 1 m. The injection and detector were set at 200°C and 220°C, respectively. Helium gas was used as the carrier gas, and the flow rate was set at 30 ml/min. The FID detector was used during this process. Methane was used to determine the column dead volume. Polar and nonpolar probes of 0.3, 0.6, 0.9, and 3 μl volumes were injected every 10°C in the range of 40-150°C. All parameters of the study were inspected by a computer software program connected to the GC-2010 brand device.

3. Results and Discussion

The specific retention volumes of the probes which are calculated from equation (1) are given in Tables 1(a) and 1(b). As seen in the tables, there is a linear relationship between probe volume and retention volume, and as the amount of probe increases, its retention volume increases. In a study performed by Munk et al., a linear relationship between the retention time of the probes and the retention volume was found in the injection range [15]. The retention time or retention volume increases with the injection volume linearly [16]. The physical and thermodynamic values obtained from all three probe quantities (belonging to the polymer-probe system) were found to be close to each other and within acceptable limits. Repeatable results were not obtained at 3 μl injection, and the detector was extinguished at the end of a few injections. As a result, low-volume injections were the preferred choice for achieving accurate results for the polymer-solvent system. The glass transition temperatures of the polymers (), the solubility parameters (), the adsorption temperatures on the polymers under the glass transition temperature of the probes (), enthalpies of sorption (), free energies (), entropy (), enthalpy partial molar free energies (), weight fraction activity coefficients, , and Florry-Huggins interaction parameters () were calculated.

Table 1

(a) For the CHMMA polymer, the specific retention volume values of alcohols (cm³/g) are calculated over the period of retention between 313 and 423 K

(K)
Ethyl alcohol
1-Propyl alcohol
1-Butyl alcohol
1-Pentyl alcohol

Probe volume
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl

423
8,781
9,151
9,178
10,088
10,124
10,146
10,917
11,457
11,939
14,303
14,7
14,843

413
9,623
10,207
9,997
11,727
11,921
11,777
13,48
13,597
13,595
18,467
19,012
18,632

403
10,096
10,54
10,903
12,236
12,6
12,761
16,275
16,517
16,961
22,979
23,284
23,786

393
11,146
11,404
12,093
14,201
14,503
14,718
19,065
19,323
17,667
27,979
29,264
29,824

383
11,914
12,372
13,059
16,084
16,267
16,496
22,591
22,682
21,186
34,184
36,979
38,079

373
14,489
14,636
15,225
18,221
18,762
19,155
26,08
26,767
27,897
43,614
46,365
47,887

363
16,839
17,259
17,574
20,459
20,879
21,141
31,161
33,254
34,046
61,745
67,254
69,824

353
18,694
19,595
19,877
23,762
24,269
25,226
36,826
39,079
42,968
75,23
80,917
88,238

343
21,039
21,566
22,111
26,48
27,261
30,896
45,343
46,95
55,128
85,73
98,928
111,832

333
21,3
21,33
22,528
27,403
27,505
32,155
44,905
49,523
61,957
91,04
104,534
122,672

323
26,109
27,927
31,128
34,473
42,037
43,419
56,655
68,728
93,893
121,312
151,785
193,532

313
32,81
34,624
38,174
51,187
54,027
63,728
73,463
112,629
131,006
226,599
243,399
317,696

(b) For the CHMMA polymer, the specific retention volume values of alkanes (cm³/g) are calculated over the period of retention between 313 and 423 K

(K)
n-Hexane
n-Heptane
n-Octane
n-Nonane

Probe volume
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl

423
10,7
10,953
11,831
8,935
9,403
10,003
9,475
10,376
11,007
11,385
12,394
12,979

413
12,389
12,701
12,762
10,051
10,246
10,982
11,493
12,072
12,345
14,415
14,921
15,375

403
13,044
13,205
13,569
10,742
10,903
11,792
12,196
12,519
13,449
15,305
15,709
16,598

393
13,986
14,546
14,89
11,619
11,834
12,695
13,082
13,599
14,46
16,698
17,042
18,075

383
14,938
15,305
15,58
12,555
12,739
13,655
14,205
14,709
15,58
19,016
19,52
20,208

373
16,208
16,553
17,092
13,604
13,752
15,127
15,324
16,453
16,748
20,923
21,856
22,838

363
17,731
17,836
18,361
14,741
15,265
16,525
17,731
18,203
19,095
24,341
24,918
27,803

353
19,145
19,595
19,877
16,498
17,625
18,019
19,708
20,271
20,947
27,38
30,801
33,223

343
21,039
22,293
23,868
18,077
19,99
20,536
22,611
25,171
24,383
34,4
39,287
42,467

333
21,044
22,213
23,528
18,8
20,776
21,567
25,162
27,44
28,717
40,134
45,8
50,356

323
25,091
27,709
30,4
24,436
26,4
28,581
36,437
40,655
43,783
67,056
67,71
78,401

313
33,284
33,757
39,12
32,81
35,886
40,382
59,39
65,7
67,277
112,55
135,096
147,618

As shown in Figures 1(a)–1(c), the glass transition temperature of the CHMMA polymer in the graphs , 1/T drawn for each of the three injections was found to be about 60°C.As shown in Table 2, the adsorption heats () on the CHMMA polymer of the probes under glass transition temperatures, negative values, indicate that all probes interact with the polymer. While the values of were found to be positive in the area of sorption on above 353-383 K, and were found to be negative, as seen in Tables 3–5. These values are in agreement with the polymer-nonsolvent systems [5]. The positive values of and and the negative values of are compatible with previously published works about dioxolane ring containing polymer-probe systems [17]. Thermodynamic data for the infinite dilution state are supportive for polymer-nonsolvent systems. As can seen be in Table 6, partial molar free energies increased with the increase in the number of carbons in the probs. But, in all probes, decreased with increasing column temperature. Partial molar enthalpy () values of the mixture of infinitely dilute from data given in Table 7 between 393 and 423 K were found. values were calculated from the slope of the lines given in Figures 2–4 according to equation (5). As seen in Table 8, the enthalpy () values of the infinite diluted state, calculated from all three injections, are positive as they should be in polymer-nonsolvent systems [18]. Whether probes can solve the polymer can be understood from the relationship given below [19]. According to the following:

(i): good solvent(ii): moderate solvent(iii): bad solvent

(a)

(b)

(c)

Figure 1: (a) Change in logarithmic specific retention volume with temperature between temperatures 313 and 423 K (for 0.3 μl prop). (b) Change in logarithmic specific retention volume with temperature between temperatures (for 0,6 μl prop). (c) Change in logarithmic specific retention volume with temperature between temperatures (for 0,9 μl prop).

Table 2: The adsorption heats of the different amounts of the probes on the CHMMA polymer.

Probes
(J/mol)

0,3 μl
0,6 μl
0,9 μl

Ethyl alcohol
−4378,30
−9528,3
−13749

1-Propyl alcohol
−20754,68
−25424
−32873

1-Butyl alcohol
−48243,53
−39060
−25241

1-Pentyl alcohol
−4780,11
−40085
−50643

n-Hexane
−16998,41
−12877
−21874

n-Heptane
−21746,03
−22903
−33799

n-Octane
−51405,70
−52800
−50547

n-Nonane
−58870,43
−71339
−70607

Table 3: The free energy of the sorption of the probe-CHMMA polymer system.

(K)
(J/mol)

353
363
373
383

0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl

Ethyl alcohol
9567,22
9428,98
9387,02
10153,8
10079,4
10024,8
10900
10868,6
10746,2
11815,7
11695,5
11523,3

1-Propyl alcohol
8082,18
8082,18
7906,6
8763,1
8763,1
8664,08
9363,99
9363,99
9208,87
10012,5
10012,5
9931,93

1-Butyl alcohol
6179,52
6005,13
5726,53
6859
6662,69
6591,61
7600,29
7519,61
7391,3
8261,65
8248,84
8466,25

1-Pentyl alcohol
3572,75
3358,75
3104,39
4270,5
4012,41
3899,16
5466,87
5277,07
5176,84
6389,67
6139,26
6045,86

n-Hexane
7658,05
7589,82
7547,86
8106,7
8088,86
8001,26
8608,71
8608,71
8608,71
9099,49
9099,49
9099,49

n-Heptane
7652,17
7458,12
7393,2
8209
8103,52
7864,01
8684,23
8650,65
8354,94
9172,73
9126,37
8905,13

n-Octane
6745,33
6662,62
6566,28
7255,65
7176,31
7031,84
7908,25
7687,66
7632,52
8361,86
8250,78
8067,48

n-Nonane
5439,67
5093,92
4871,63
5949,05
5878,3
5547,47
6582,47
6447,1
6310,72
7063,45
6980,1
6869,73

Table 4: The sorption-related entropy values of the probe-CHMMA polymer system.

(K)
(J/mol)

353
363
373
383

0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl

Ethyl alcohol
−26386,08
−26774
−25175
−26973
−27424
−25813
−27719
−28213
−26534
−28635
−29040
−27311

1-Propyl alcohol
−22544,22
−22780
−23359
−23225
−23461
−24117
−23826
−24062
−24662
−24475
−24711
−25385

1-Butyl alcohol
−24653,90
−26790
−31783
−25333
−27447
−32648
−26075
−28304
−33448
−26736
−29033
−34523

1-Pentyl alcohol
−34067,51
−33911
−35676
−34765
−34565
−36470
−35962
−35829
−37748
−36884
−36691
−38617

n-Hexane
−17019,61
−16762
−16568
−17468
−17261
−17021
−17970
−17781
−17628
−18461
−18271
−18119

n-Heptane
−17789,91
−19607
−17726
−18347
−20253
−18197
−18822
−20800
−18688
−19310
−21276
−19238

n-Octane
−19433,73
−18621
−18035
−19944
−19134
−18501
−20597
−19646
−19101
−21050
−20209
−19536

n-Nonane
−19460,79
−22053
−23883
−19970
−22837
−24558
−20604
−23406
−25322
−21085
−23939
−25881

Table 5: The free enthalpy values of the probe-CHMMA polymer system.

Probes
(J/mol)

0,3 μl
0,6 μl
0,9 μl

Ethyl alcohol
−16818,87
−17345
−15788

1-Propyl alcohol
−14462,04
−14698
−15453

1-Butyl alcohol
−18474,38
−20785
−26056

1-Pentyl alcohol
−30494,75
−30552
−32571

n-Hexane
−9361,56
−9171,9
−9019,6

n-Heptane
−10137,74
−12149
−10333

n-Octane
−12688,40
−11958
−11469

n-Nonane
−14021,13
−16959
−19011

Table 6: Partial molar free energy values of the infinite dilution state.

(K)
(J/mol)

393
403
413
423

0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl

Ethyl alcohol
7598,17
7522,97
7333,34
7120,98
6973,46
6862,83
6486,82
6284,11
6356,26
6021,02
5876,75
5866,19

1-Propyl alcohol
8101,66
8033,00
7983,96
7754,62
7657,40
7613,81
7081,22
7022,81
7067,48
6805,76
6791,69
6784,65

1-Butyl alcohol
8784,97
8739,20
9033,45
8398,33
8348,04
8441,91
8156,63
8125,71
8125,71
8040,94
7872,03
7727,74

1-Pentyl alcohol
9262,31
9115,18
9053,06
8971,63
8928,05
8857,64
8812,87
8713,23
8781,95
8836,23
8741,22
8706,03

n-Hexane
5083,97
4956,46
4881,26
4707,09
4666,85
4572,98
4281,03
4195,13
4181,39
4702,29
4607,85
4304,86

n-Heptane
7742,02
6659,84
7454,31
7365,72
6829,30
7053,92
6967,84
6380,31
6662,05
6767,05
6327,18
6369,41

n-Octane
9386,55
8111,47
9059,60
8924,69
7908,84
8596,13
8445,24
7868,02
8201,30
8456,18
7787,57
7928,33

n-Nonane
10612,58
8778,43
10351,03
10138,34
8733,59
9866,78
9599,68
8647,95
9376,35
9698,39
8797,53
9237,40

Table 7: The weight fraction activity coefficients of the probe-CHMMA polymer system for the infinite dilution state.

(K)
423
413
403
393

0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl

Ethyl alcohol
1,711
1,67
1,667
1,888
1,829
1,85
2,124
2,08
2,047
2,324
2,301
2,243

1-Propyl alcohol
1,934
1,93
1,928
2,061
2,044
2,057
2,313
2,284
2,271
2,478
2,457
2,442

1-Butyl alcohol
2,285
2,237
2,196
2,374
2,365
2,365
2,505
2,49
2,518
2,687
2,673
2,763

1-Pentyl alcohol
2,511
2,484
2,474
2,565
2,536
2,556
2,676
2,663
2,642
2,833
2,788
2,769

n-Hexane
1,195
1,171
1,094
1,246
1,221
1,217
1,404
1,392
1,364
1,555
1,516
1,493

n-Heptane
1,923
1,798
1,81
2,028
1,857
1,939
2,197
2,037
2,104
2,368
2,037
2,28

n-Octane
2,403
2,213
2,253
2,458
2,29
2,387
2,662
2,359
2,564
2,871
2,481
2,771

n-Nonane
2,756
2,5
2,625
2,794
2,517
2,729
3,024
2,605
2,943
3,246
2,685
3,166

Figure 2: The graph of ; 1/T calculated from 0.3 μl probe injection.

Figure 3: The graph of ; 1/T calculated from 0.6 μl probe injection.

Figure 4: The graph of ; 1/T calculated from 0.9 μl probe injection.

Table 8: The partial molar enthalpy of mixing of poly(CHMMA) with alkanes and alcohols.

Probes
(J/mol)

0,3 μl
0,6 μl
0,9 μl

Ethyl alcohol
28701,14
29681,97
26621,35

1-Propyl alcohol
26070,62
25213,75
24303,63

1-Butyl alcohol
18546,76
19848,71
25682,95

1-Pentyl alcohol
14883,83
14412,96
13454,60

n-Hexane
17182,42
16721,53
18440,27

n-Heptane
20837,03
12358,96
21805,38

n-Octane
22333,65
12099,40
23980,01

n-Nonane
23625,62
8931,46
25475,80

It has been found that alkane and alcohols (CHMMA) used as probes are bad solvents at low temperatures for the polymer. As shown in Tables 9 and 10, at high temperatures, alkanes can solve the polymer better than alcohols and this result is understood from the Flory-Huggins () parameters and the weight fraction activity coefficients, . The Flory-Huggins () value must be less than 0.5 in order for the probes to resolve the polymer. At high temperatures, the solubility parameters () of the probes and the solubility parameters () of the polymers were calculated. The difference between solubility parameters () must be less than 2 for the probe to be capable of solving the polymer [20]. The solubility parameter of a polymer, (), can be determined from either the slope or the intercept of a straight line obtained by plotting the left-hand side of equation (10) [10]. The values found in Tables 11 and 12 were used to determine the solubility parameter of the polymer. The solubility parameter of poly(CHMMA) was determined from either the slope or intercepts shown in Figures 5(a), 6(a), and 7(a), 5.922 (cal/cm³)0.5 or 6.617 (cal/cm³)0.5, 5.933 (cal/cm³)0.5 or 6.608 (cal/cm³)0.5, and 5.904 (cal/cm³)0.5 or 6.561 (cal/cm³)0.5 at 423 K, respectively. In addition, the solubility parameters of the polymer calculated at 413 K were found from the slopes and intercept of the lines in Figures 5(b), 6(b), and 7(b). The solubility parameter values of the polymer calculated for each of the three injections given in Table 13 are similar.

Table 9: Flory-Huggins interaction parameters of the alcohols-CHMMA polymer system.

(K)

Ethyl alcohol
1-Propyl alcohol
1-Butyl alcohol
1-Pentyl alcohol

0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl

423
0,302
0,261
0,258
0,533
0,529
0,527
0,899
0,85
0,809
1,142
1,114
1,104

413
0,482
0,423
0,444
0,664
0,648
0,66
0,993
0,984
0,984
1,203
1,174
1,194

403
0,723
0,68
0,646
0,923
0,894
0,881
1,13
1,115
1,089
1,322
1,309
1,288

393
0,931
0,908
0,849
1,095
1,074
1,059
1,32
1,307
1,396
1,487
1,442
1,423

383
1,189
1,152
1,098
1,313
1,302
1,288
1,523
1,519
1,587
1,675
1,596
1,567

373
1,34
1,329
1,29
1,555
1,526
1,505
1,779
1,7535
1,712
1,848
1,787
1,754

363
1,557
1,532
1,514
1,832
1,812
1,799
2,031
1,966
1,942
1,949
1,864
1,826

353
1,844
1,797
1,783
2,104
2,083
2,044
2,327
2,267
2,172
2,236
2,163
2,076

343
2,144
2,119
2,094
2,449
2,42
2,295
2,618
2,583
2,423
2,63
2,487
2,364

333
2,577
2,576
2,521
2,904
2,9
2,744
3,169
3,071
2,847
3,14
3,002
2,842

323
2,851
2,784
2,675
3,202
3,004
2,972
3,524
3,33
3,018
3,474
3,25
3,007

313
3,134
3,081
2,983
3,38
3,326
3,161
3,904
3,477
3,326
3,529
3,458
3,191

Table 10: Flory-Huggins interaction parameters of the alkanes-CHMMA polymer system.

(K)

n-Hexane
n-Heptane
n-Octane
n-Nonane

0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl

423
−0,306
−0,33
−0,407
0,43
0,379
0,317
0,915
0,825
0,766
1,253
1,168
1,122

413
−0,255
−0,28
−0,285
0,537
0,517
0,448
0,974
0,925
0,902
1,295
1,261
1,231

403
−0,0983
−0,11
−0,137
0,708
0,693
0,614
1,181
1,155
1,083
1,532
1,505
1,45

393
0,0538
0,014
−0,008
0,881
0,863
0,793
1,395
1,356
1,294
1,759
1,739
1,68

383
0,223
0,199
0,181
1,072
1,058
0,988
1,614
1,579
1,522
1,964
1,938
1,904

373
0,393
0,372
0,339
1,278
1,267
1,172
1,86
1,789
1,771
2,226
2,183
2,139

363
0,57
0,564
0,535
1,503
1,468
1,388
2,058
2,031
1,984
2,457
2,434
2,324

353
0,779
0,756
0,742
1,716
1,65
1,628
2,32
2,291
2,259
2,749
2,631
2,556

343
0,991
0,933
0,865
1,974
1,873
1,847
2,576
2,469
2,501
2,96
2,827
2,75

333
1,319
1,265
1,207
2,31
2,21
2,172
2,893
2,806
2,761
3,279
3,147
3,052

323
1,495
1,396
1,303
2,451
2,37
2,294
2,978
2,869
2,795
3,275
3,266
3,119

313
1,592
1,578
1,43
2,591
2,501
2,383
2,982
2,881
2,857
3,309
3,126
3,038

Table 11: The values calculated from equation (10).

(K)

413
423

0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl

Ethyl alcohol
72,699
73,374
73,136
67,812
68,285
68,319

1-Propyl alcohol
69,031
69,18
69,07
64,671
64,703
64,723

1-Butyl alcohol
63,606
63,672
63,671
57,875
60,294
60,609

1-Pentyl alcohol
61,224
61,416
61,283
59,926
58,057
58,121

n-Hexane
22,295
22,422
22,447
20,232
20,351
20,745

n-Heptane
24,17
28,389
24,587
22,542
22,784
23,076

n-Octane
26,673
24,261
26,982
24,929
25,323
25,58

n-Nonane
28,255
26,885
28,506
26,561
26,895
27,076

Table 12: Solubility parameters of the probes between 413 and 423 K.

(K)
413
423

Ethyl alcohol
9.713
9.35

1-Propyl alcohol
9.313
9.067

1-Butyl alcohol
9.033
8.794

1-Pentyl alcohol
8.839
8.634

n-Hexane
5.353
5.131

n-Heptane
5.806
5.623

n-Octane
6.106
5.947

n-Nonane
6.255
6.113

(a)

(b)

Figure 5: (a) The graph of 423 K ; infinitely diluted state calculated from 0.3 μl probe injection. (b) The graph of 413 K ; infinitely diluted state calculated from 0.3 μl probe injection.

(a)

(b)

Figure 6: (a) The graph of 423 K ; infinitely diluted state calculated from 0.6 μl probe injection. (b) The graph of 413 K ; infinitely diluted state calculated from 0.6 μl probe injection.

(a)

(b)

Figure 7: (a) The graph of 423°K ; infinitely diluted state calculated from 0.9 μl probe injection. (b) The graph of 423°K ; infinitely diluted state calculated from 0.9 μl probe injection.

Table 13: Solubility parameters of the polymer (CHMMA) calculated from the slope and intercept.

(K)
Slope
Intercept
(J/cm³)1/2

From slope
From intercept

0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl
0,3 μl
0,6 μl
0,9 μl

423
11,845
11,867
11,809
43,786
43,678
43,053
24,794
24,840
24,719
27,704
27,666
27,470

413
12,205
12,191
12,177
46,256
45,947
45,827
25,548
29,119
25,489
28,474
28,378
28,340

4. Conclusion

As a result, characterization of polymeric materials and thermodynamic information of polymer-probe systems can be obtained easily, quickly, and economically with inverse gas chromatography technique. It was observed that the specific retention volume was linearly changed with the amount of the probe. The specific retention volume was found to be independent of the physical and chemical properties of the probes. Results are suitable for polymer-nonsolvent systems. It was observed that the physicochemical results obtained from the retention volume values of the probes in the volume of 0.3, 0.6, and 0.9 μl were close to each other and within acceptable limits. Additionally, the injections of probes in the volume of 3 μl was tried but no reproducible results were obtained and it has been observed that the detector went out after a few injections. As the amount of probes increases, it is difficult to obtain reproducible results. For this reason, low-volume injections may be preferred both for achieving correct results and for saving time and substances.

Data Availability

The data used to support the findings of this study are available from the corresponding author upon request.

Conflicts of Interest

The author declares that they have no conflicts of interest.

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