Research ArticleInvestigation of the Specific Retention Volume of the ProbeVolume and the Effects on the Polymer-Probe System by InverseGas 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 AttributionLicense, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work isproperly cited.

In this study, the effects of probe quantities on retention volume and the physical and thermodynamic results of polymer-probesystems were investigated. For this purpose, by using inverse gas chromatographic method. Alcohols and alkanes with differentchemical and physical properties were injected as probes on homopolymer (2-cyclohexylidene-1,3-dioxolane-4-yl-methylmethacrylate) (CHMMA). Probe quantities of 0.3, 0.6, and 0.9 μl were selected, and an injection was made at every 10°Cbetween 40 and 150°C. In addition, 3 μl volume probes were tried but reproducible results were not obtained in these volumesand the detector was observed to be out of order after several injections. It has been observed that the specific retention volumeof alcohols and alkanes partially increased by increasing the injection amount. A linear relationship was observed between probequantities and specific retention volume. This linear relationship is apparent from the specific retention volume values, wherethe probes are independent of the physical and chemical structures. It was observed that the results obtained in all threeinjections were close to each other and within acceptable limits. The glass transition temperature of the polymer was determinedto be a Tg 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 usedmethod for studying the physicochemical and surface prop-erties of polymer-solvent systems of polymers. The methodis simple, economical, fast, and accurate.

The IGC method developed by Smidsrod and Guillet wasused successfully to determine the physicochemical and sur-face properties of polymeric materials [1]. Many parameterssuch as glass transition temperatures, adsorption heats, theweight fraction activity coefficients, free energies, enthalpiesof mixing, solubility parameters, interaction parameter, dif-fusion coefficient, and surface properties of the polymerscan be calculated with this method [2, 3]. Vinyl polymerscontaining the 1,3-dioxane group in their structure havemany properties such as negative electron beam, good

resistance to dry etching, and herbicide function [4]. Prop-erties of poly (acetyl benzofuran methyl methacrylate) andcopolymers made by acrylonitrile are investigated byinverse gas chromatography. The properties of these struc-turally similar polymers were successfully determined byinverse gas chromatography [5]. The solubility and surfacethermodynamics of the polypyrrole chloride were investi-gated by inverse gas chromatography, and some probesinteracted with the polymer but all probes did not dissolvethe polymer [6].

In this study, physicochemical properties of poly(2-cyclohex-ylidene-1,3-dioxolane-4-yl-methyl methacrylate) (CHMMA)were investigated by inverse gas chromatography. In addi-tion, the effect of the probe quantity on the retention vol-ume and polymer-probe system was investigated. Thebasis of the method is to find out the retention time of

HindawiInternational Journal of Polymer ScienceVolume 2019, Article ID 5623873, 11 pageshttps://doi.org/10.1155/2019/5623873

the probe injected into the column as a function of time,after the polymers to be examined have been coated witha supporting sheath.

2. Materials and Methods

The probe specific retention volumes, V0g, are calculated from

the standard chromatographic relation [7]:

Vg0 = F 273, 2 tr

w T 3/2 × Pi/Po2 – 1

Pi/Po3 – 1

, 1

where tr is the retention times of the probe, F is the flowrate of the carrier gas measured at room temperature, Wis the mass of the polymeric stationary phase, T is the col-umn temperature, and Pi and Po are inlet and outlet pres-sures, respectively.

The molar heat (enthalpy) (ΔH1S) and the molar free

energy (ΔG1S) of sorption of the probe absorbed by the poly-

mer are given by the following equation [8]:

ΔH1S =

−R∂Vg0

∂ 1/T ,

ΔG1S = −RT ln

M1Vg0

273 2R

2

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

ΔG1S = ΔH1

S − TΔS1S, 3

where Vg0 is the probe specific retention volume, T is the col-

umn temperature (K), M is the molecular weight of theprobe, and R is the gas constant. The adsorption enthalpyof probes adsorbed by the polymer, ΔHa, is given by the fol-lowing equation [9]:

∂Vg0

∂ 1/T = −ΔHaR

4

Partial molar free energy of mixing ΔG∞1 (cal/mol) and

partial molar entalphy ΔH∞1 (cal/mol) at infinite dilution

are calculated according to the following equations [10]:

ΔH1∞ = R

δ ln a1/w1∞

δ 1/T , 5

ΔG1∞ = R ln a1

w1

∞6

The weight fraction activity coefficient,Ω1∞, of the solute

probe at infinite dilution is calculated according to the fol-lowing equation [11]:

Ω1∞ = 273 2R

Vg0P1

0M1 exp −P10 B11 –V1 /RT

7

The polymer-solute interaction parameter χ∞12 , at infinite

dilution of different solutes used in this work, is defined bythe following equation:

χ12∞ =

ln 273 2 × R ×V2 / Vg0 ×V1 × P0

1 – 1 – P01

RT B11 −V1,

8

where R is the gas constant, V2 is the specific volume of thepolymer, V1 is the molar volume of the solute, P1

0 is thevapor pressure, and B11 is the second virial coefficient ofthe solute in the gaseous state. V1, P1

0, and B11 were calcu-lated at the column temperature.

Second virial coefficients, B11, were computed using thefollowing equation [12]:

B11Vc

= 0 430 − 0 886 TcT

− 0 694 TcT

2− 0 375 n − 1 Tc

T

4 5,

9

where V c and Tc are the critical molar volume and thecritical temperature of the solute, respectively, and n isthe number of carbon atoms in the solute.

The solubility parameters of polymers, δ2, can be deter-mined by using the following relation:

δ12 − ΔG1

∞

V1= 2δ1δ2 − δ2

2, 10

δ12

RT−χ12

∞

V1= 2δ2

RTδ1 −

δ22

RT11

If the left-hand side of this equation is plotted against δ1,then a straight line with a slope of (2δ1δ2) and an inter-cept of −δ2

2 is obtained. Solubility parameters of the poly-mer, δ2, can be calculated from both the slope andintercept of the straight line [13].

Ethyl alcohol, 1-propyl alcohol, 1-butyl alcohol, 1-pentylalcohol, n-hexane, n-heptane, n-octane, and n-nonane wereused as probes in chromatographic purity from the Merck& Company. Chromosorb W (80-100 Mesh) from thePolymer SIĞMA Company was coated 10% by weight onthe polymer. The coated polymer weight is 0.228 grams.The 2-cyclohexylidene-1,3-dioxolane-4-yl-methyl methacry-late (CHMMA) polymer used in the experiment was synthe-sized for the first time in the laboratory of the Department ofChemistry of Fırat University [14]. GC-2010 model Shi-madzu brand gas chromatography was performed by addingapparatus suitable for filled column analysis. This column is apolymer steel barrel with a diameter of 3.2mm and a lengthof 1m. The injection and detector were set at 200°C and220°C, respectively. Helium gas was used as the carrier gas,and the flow rate was set at 30ml/min. The FID detectorwas used during this process. Methane was used to determinethe column dead volume. Polar and nonpolar probes of 0.3,0.6, 0.9, and 3 μl volumes were injected every 10°C in therange of 40-150°C. All parameters of the study were

2 International Journal of Polymer Science

inspected by a computer software program connected to theGC-2010 brand device.

3. Results and Discussion

The specific retention volumes of the probes which are calcu-lated from equation (1) are given in Tables 1(a) and 1(b). Asseen in the tables, there is a linear relationship between probevolume and retention volume, and as the amount of probeincreases, its retention volume increases. In a study per-formed by Munk et al., a linear relationship between theretention time of the probes and the retention volume wasfound in the injection range [15]. The retention time orretention volume increases with the injection volume linearly[16]. The physical and thermodynamic values obtained fromall three probe quantities (belonging to the polymer-probesystem) were found to be close to each other and within

acceptable limits. Repeatable results were not obtained at3 μl injection, and the detector was extinguished at the endof a few injections. As a result, low-volume injections werethe preferred choice for achieving accurate results for thepolymer-solvent system. The glass transition temperaturesof the polymers (Tg), the solubility parameters (δ2), theadsorption temperatures on the polymers under the glasstransition temperature of the probes (ΔHa), enthalpies ofsorption (ΔH1

S), free energies (ΔG1S), entropy (ΔS1

S),enthalpy partial molar free energies (ΔG1

∞), weight fractionactivity coefficients, Ω1

∞, and Florry-Huggins interactionparameters (χ) were calculated.

As shown in Figures 1(a)–1(c), the glass transition tem-perature Tg of the CHMMA polymer in the graphs ln Vg0,1/T drawn for each of the three injections was found to beabout 60°C.As shown in Table 2, the adsorption heats (ΔHa)on the CHMMA polymer of the probes under glass transition

Table 1

(a) For the CHMMA polymer, the specific retention volume values of alcohols V0g (cm

3/g) are calculated over the period of retention between313 and 423K

T (K) Ethyl alcohol 1-Propyl alcohol 1-Butyl alcohol 1-Pentyl alcoholProbe 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 V0g (cm

3/g) are calculated over the period of retention between313 and 423K

T (K) n-Hexane n-Heptane n-Octane n-NonaneProbe 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

3International Journal of Polymer Science

temperatures, negative values, indicate that all probes interactwith the polymer. While the values of ΔG1

S were found to bepositive in the area of sorption on Tg above 353-383K, ΔS1

S

and ΔH1S were found to be negative, as seen in Tables 3–5.

These values are in agreement with the polymer-nonsolventsystems [5]. The positive values of ΔH1

S and ΔG1S and the

negative values of ΔSS1 are compatible with previously pub-lished works about dioxolane ring containing polymer-probesystems [17]. Thermodynamic data for the infinite dilutionstate are supportive for polymer-nonsolvent systems. As canseen be in Table 6, partial molar free energies ΔG1

∞ increasedwith the increase in the number of carbons in the probs. But,in all probes, ΔG1

∞decreased with increasing column temper-ature. Partial molar enthalpy (ΔH1

∞) values of the mixture ofinfinitely dilute from ln a1/w1

∞ data given in Table 7between 393 and 423K were found. ΔH1

∞ values were cal-culated from the slope of the lines given in Figures 2–4according to equation (5). As seen in Table 8, the enthalpy(ΔH1

∞) values of the infinite diluted state, calculated fromall three injections, are positive as they should be inpolymer-nonsolvent systems [18]. Whether probes can solvethe polymer can be understood from the relationship givenbelow [19]. According to the following:

(i) Ω1∞ < 5: good solvent

(ii) 5 <Ω1∞ < 10: moderate solvent

(iii) Ω1∞ > 10: bad solvent

0.00280 0.00300 0.00320 0.003401/T

1.52

2.53

3.54

4.55

5.56

0.00220 0.00240 0.00260

Ethyl alcohol1-Propyl alcohol1-Butyl alcohol1-Pentyl alcohol

n-Hexanen-Heptanen-Octanen-Nonane

lnV

g

(a)

lnV

g

0.00280 0.00300 0.00320 0.003401/T

1.52

2.53

3.54

4.55

5.56

0.00220 0.00240 0.00260

Ethyl alcohol1-Propyl alcohol1-Butyl alcohol1-Pentyl alcohol

n-Hexanen-Heptanen-Octanen-Nonane

(b)

lnV

g

0.00280 0.00300 0.00320 0.003401/T

1.52

2.53

3.54

4.55

5.56

0.00220 0.00240 0.00260

Ethyl alcohol1-Propyl alcohol1-Butyl alcohol1-Pentyl alcohol

n-Hexanen-Heptanen-Octanen-Nonane

(c)

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

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

ProbesΔHa (J/mol)

0,3 μl 0,6 μl 0,9 μl

Ethyl alcohol −4378,30 −9528,3 −137491-Propyl alcohol −20754,68 −25424 −328731-Butyl alcohol −48243,53 −39060 −252411-Pentyl alcohol −4780,11 −40085 −50643n-Hexane −16998,41 −12877 −21874n-Heptane −21746,03 −22903 −33799n-Octane −51405,70 −52800 −50547n-Nonane −58870,43 −71339 −70607

4 International Journal of Polymer Science

It has been found that alkane and alcohols (CHMMA)used as probes are bad solvents at low temperatures for thepolymer. As shown in Tables 9 and 10, at high temperatures,alkanes can solve the polymer better than alcohols and thisresult is understood from the Flory-Huggins (χ) parametersand the weight fraction activity coefficients, Ω1

∞. TheFlory-Huggins (χ) value must be less than 0.5 in order forthe probes to resolve the polymer. At high temperatures,the solubility parameters (δ1) of the probes and the solubility

parameters (δ2) of the polymers were calculated. The differ-ence between solubility parameters (δ1 − δ2) must be lessthan 2 for the probe to be capable of solving the polymer[20]. The solubility parameter of a polymer, (δ2), can bedetermined from either the slope or the intercept of a straightline obtained by plotting the left-hand side of equation (10)[10]. The values found in Tables 11 and 12 were used todetermine the solubility parameter of the polymer. The solu-bility parameter of poly(CHMMA) was determined fromeither 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 or6.561 (cal/cm3)0.5 at 423K, respectively. In addition, the sol-ubility parameters of the polymer calculated at 413K werefound from the slopes and intercept of the lines inFigures 5(b), 6(b), and 7(b). The solubility parameter valuesof the polymer calculated for each of the three injectionsgiven in Table 13 are similar.

4. Conclusion

As a result, characterization of polymeric materials andthermodynamic information of polymer-probe systemscan be obtained easily, quickly, and economically withinverse gas chromatography technique. It was observed

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

T (K)ΔGS

1 (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.

T (K)T ΔSS1 (J/mol)

353 363 373 3830,3 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 −273111-Propyl alcohol −22544,22 −22780 −23359 −23225 −23461 −24117 −23826 −24062 −24662 −24475 −24711 −253851-Butyl alcohol −24653,90 −26790 −31783 −25333 −27447 −32648 −26075 −28304 −33448 −26736 −29033 −345231-Pentyl alcohol −34067,51 −33911 −35676 −34765 −34565 −36470 −35962 −35829 −37748 −36884 −36691 −38617n-Hexane −17019,61 −16762 −16568 −17468 −17261 −17021 −17970 −17781 −17628 −18461 −18271 −18119n-Heptane −17789,91 −19607 −17726 −18347 −20253 −18197 −18822 −20800 −18688 −19310 −21276 −19238n-Octane −19433,73 −18621 −18035 −19944 −19134 −18501 −20597 −19646 −19101 −21050 −20209 −19536n-Nonane −19460,79 −22053 −23883 −19970 −22837 −24558 −20604 −23406 −25322 −21085 −23939 −25881

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

Probes ΔHS1 (J/mol)

0,3 μl 0,6 μl 0,9 μl

Ethyl alcohol −16818,87 −17345 −157881-Propyl alcohol −14462,04 −14698 −154531-Butyl alcohol −18474,38 −20785 −260561-Pentyl alcohol −30494,75 −30552 −32571n-Hexane −9361,56 −9171,9 −9019,6n-Heptane −10137,74 −12149 −10333n-Octane −12688,40 −11958 −11469n-Nonane −14021,13 −16959 −19011

5International Journal of Polymer Science

Table6:Partialmolar

free

energy

values

oftheinfinitedilution

state.

T(K

)ΔG∞ 1

(J/m

ol)

393

403

413

423

0,3μl

0,6μl

0,9μl

0,3μl

0,6μl

0,9μl

0,3μl

0,6μl

0,9μl

0,3μl

0,6μl

0,9μl

Ethylalcoho

l7598,17

7522,97

7333,34

7120,98

6973,46

6862,83

6486,82

6284,11

6356,26

6021,02

5876,75

5866,19

1-Propylalcoh

ol8101,66

8033,00

7983,96

7754,62

7657,40

7613,81

7081,22

7022,81

7067,48

6805,76

6791,69

6784,65

1-Butylalcoho

l8784,97

8739,20

9033,45

8398,33

8348,04

8441,91

8156,63

8125,71

8125,71

8040,94

7872,03

7727,74

1-Pentylalcoh

ol9262,31

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-Non

ane

10612,58

8778,43

10351,03

10138,34

8733,59

9866,78

9599,68

8647,95

9376,35

9698,39

8797,53

9237,40

6 International Journal of Polymer Science

Table7:The

weightfraction

activity

coeffi

cientsof

theprobe-CHMMApo

lymer

system

fortheinfinitedilution

state.

lnα w1

∞

T(K

)423

413

403

393

0,3μl

0,6μl

0,9μl

0,3μl

0,6μl

0,9μl

0,3μl

0,6μl

0,9μl

0,3μl

0,6μl

0,9μl

Ethylalcoho

l1,711

1,67

1,667

1,888

1,829

1,85

2,124

2,08

2,047

2,324

2,301

2,243

1-Propylalcoh

ol1,934

1,93

1,928

2,061

2,044

2,057

2,313

2,284

2,271

2,478

2,457

2,442

1-Butylalcoho

l2,285

2,237

2,196

2,374

2,365

2,365

2,505

2,49

2,518

2,687

2,673

2,763

1-Pentylalcoh

ol2,511

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-Non

ane

2,756

2,5

2,625

2,794

2,517

2,729

3,024

2,605

2,943

3,246

2,685

3,166

7International Journal of Polymer Science

that the specific retention volume was linearly changedwith the amount of the probe. The specific retention vol-ume was found to be independent of the physical andchemical properties of the probes. Results are suitable forpolymer-nonsolvent systems. It was observed that thephysicochemical results obtained from the retention vol-ume values of the probes in the volume of 0.3, 0.6, and0.9 μl were close to each other and within acceptablelimits. Additionally, the injections of probes in the volumeof 3μl was tried but no reproducible results were obtainedand it has been observed that the detector went out after a

0.00230 0.00240 0.00250 0.00260

y = 3450x − 6.4506R

2 = 0.9979y = 2.4028x − 3.306

R2 = 0.9455

y = 2229.4x − 3.0056R

2 = 0.9825y = 1798.1x − 1.7643

R2 = 0.9647

y = 2065.4x − 3.716R

2 = 0.9676y = 2504.7x − 4.0145

R2 = 0.9926

y = 2684.7x − 3.9864R

2 = 0.9573y = 2839.9x − 4.0108

R2 = 0.9419

ln (a

1/w1)∞

1.5

1

2

2.5

3

3.5

Ethyl alcohol

1-Propyl alcohol

1-Butyl alcohol

1-Pentyl alcohol

n-Hexane

n-Heptane

n-Octane

n-nonane

1/T

Figure 2: The graph of ln a1/w1∞; 1/T calculated from 0.3 μl

probe injection.

0.002301

1.2

1.4

1.6

1.8

2

2.2

2.4

2.6

2.8

3

0.00240 0.00250 0.00260

y = 3567.9x − 6.7813R

2 = 0.9949y = 2.4609x − 3.5588

R2 = 0.8961

y = 2385.9x − 3.4109R

2 = 0.9942y = 1732.5x − 1.6318

R2 = 0.9769

y = 2010x − 3.6053R

2 = 0.9684y = 1485.6x − 1.7118

R2 = 0.8753

y = 1454.4x − 1.2317R

2 = 0.9867y = 1073.6x − 0.0566

R2 = 0.9492

Ethyl alcohol

1-Propyl alcohol

1-Butyl alcohol

1-Pentyl alcohol

n-Hexane

n-Heptane

n-Octane

n-Nonane

1/T

ln (a

1/w1)∞

Figure 3: The graph of ln a1/w1∞; 1/T calculated from 0.6 μl

probe injection.

0.00230 0.00240 0.00250 0.00260

y = 3200x − 5.8973R

2 = 0.9999y = 1.917x − 2.3308

R2 = 0.992

y = 3087.2x − 5.1119R

2 = 0.9919y = 1617.3x − 1.3567

R2 = 0.992

y = 2233.9x − 4.1874R

2 = 0.9989y = 2621.1x − 4.3959

R2 = 0.9977

y = 2882.5x − 4.5765R

2 = 0.9947y = 3062.3x − 4.6456

R2 = 0.9823

Ethyl alcohol

1-Propyl alcohol

1-Butyl alcohol

1-Pentyl alcohol

n-Hexane

n-Heptane

n-Octane

n-Nonane

1/T

1

1.5

2

2.5

3

3.5

ln (a

1/w1)∞

Figure 4: The graph of ln a1/w1∞; 1/T calculated from 0.9 μl

probe injection.

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

ProbesΔH∞

1 (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

8 International Journal of Polymer Science

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

T (K)X∞1,2

Ethyl alcohol 1-Propyl alcohol 1-Butyl alcohol 1-Pentyl alcohol0,3 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.

T (K)X∞1,2

n-Hexane n-Heptane n-Octane n-Nonane0,3 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 δ21 − ΔG∞1 /V1 values calculated from equation (10).

T (K)δ21 − ΔG∞

1 /V1413 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 and423K.

T (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

9International Journal of Polymer Science

20

10

20

30

40

50

60

70

80

4 6 8 10

𝛿1

423 K

(𝛿12 −

𝛥G

1∞/V

1)

y = 11.845 x − 43.786R

2 = 0.991

(a)

2.50

10

20

30

40

50

60

70

80

4.5 6.5 8.5 10.5

𝛿1

413 K y = 12.205 x − 46.256R

2 = 0.9949

(𝛿12 −

𝛥G

1∞/V

1)

(b)

Figure 5: (a) The graph of 423K de δ12 − ΔG∞/V ; δ infinitely diluted state calculated from 0.3 μl probe injection. (b) The graph of 413K

de δ12 − ΔG1

∞/V1 ; δ1 infinitely diluted state calculated from 0.3 μl probe injection.

2 4 6 8 10

1/T

423 K

Ekse

n Ba

şlığı

0

10

20

30

40

50

60

70

80

y = 11.867 x − 43.678R

2 = 0.9941

(a)

2.5 4.5 6.5 8.5 10.5

1/T

413 Ky = 12.191 x − 45.947

R2 = 0.9847

Ekse

n Ba

şlığı

0

10

20

30

40

50

60

70

80

(b)

Figure 6: (a) The graph of 423K de δ12 − ΔG1

∞/V1 ; δ1 infinitely diluted state calculated from 0.6 μl probe injection. (b) The graph of 413Kde δ1

2 − ΔG1∞/V1 ; δ1 infinitely diluted state calculated from 0.6 μl probe injection.

20

10

20

30

40

50

60

70

80

4 6 8 10

𝛿1

423 K

(𝛿−𝛥G

1∞/V

1)

y = 11.809 x − 43.053R

2 = 0.9938

(a)

2.5 4.5 6.5 8.5 10.5

𝛿1

413 Ky = 12.177x − 45.827

R2 = 0.9951

0

10

20

30

40

50

60

70

80

(𝛿12 −

𝛥G

1∞/V

1)

(b)

Figure 7: (a) The graph of 423°K de δ12 − ΔG∞/V ; δ infinitely diluted state calculated from 0.9 μl probe injection. (b) The graph of 423°K

de δ12 − ΔG1

∞/V1 ; δ1 infinitely diluted state calculated from 0.9 μl probe injection.

10 International Journal of Polymer Science

few injections. As the amount of probes increases, it is dif-ficult to obtain reproducible results. For this reason, low-volume injections may be preferred both for achievingcorrect results and for saving time and substances.

Data Availability

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

Conflicts of Interest

The author declares that they have no conflicts of interest.

References

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[3] J. M. Braun and J. E. Guillet, “Determination of crystallinityby gas chromatography. Effect of curvilinearity of retentiondiagrams,” Macromolecules, vol. 10, no. 1, pp. 101–106,1977.

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[5] M. H. Karagöz, Ö. S. Zorer, and Z. İlter, “Analysis of physicaland thermodynamic properties of poly(2-phenyl-1,3-dioxo-lane-4-Yl-methyl-methacrylate-co-styrene) polymer withinverse gas chromatography,” Polymer-Plastics Technologyand Engineering, vol. 45, no. 7, pp. 785–789, 2006.

[6] O. K. Duaij, A. Alqhamdi, and Z. Y. al-Saigh, “Solubility andsurface thermodynamics of conducting polymers by inversegas chromatography. III: polypyrrole chloride,” Journal ofChromatography A, vol. 1291, pp. 137–145, 2013.

[7] J. E. Guillet, “Molecular probes in the study of polymer struc-ture,” Journal of Macromolecular Science: Part A - Chemistry,vol. 4, no. 7, pp. 1669–1674, 1970.

[8] M. Galin and L. Maslinko, “Gas-liquid chromatography studyof poly(vinylidene fluoride)-solvent interactions. Correlationanalysis of the partial molar enthalpy of mixing with probepolarity,” Macromolecules, vol. 18, no. 11, pp. 2192–2196,1985.

[9] A. Etxeberría, J. Alfageme, C. Uriarte, and J. J. Iruin, “Inversegas chromatography in the characterization of polymeric

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[10] G. DiPaola-Baranyi, J. E. Guillet, J. Klein, and H. E. Jeberien,“Estimation of solubility parameters for poly(vinyl acetate)by inverse gas chromatography,” Journal of ChromatographyA, vol. 166, no. 2, pp. 349–356, 1978.

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[13] G. DiPaola-Baranyi, “Estimation of polymer solubility param-eters by inverse gas chromatography,”Macromolecules, vol. 15,no. 2, pp. 622–624, 1982.

[14] Z. İlter, M. Çoşkun, İ. Erol, A. Ünal, and M. Ahmedzade,“Thermal behaviour of some polymethacrylates with a 1,3-dioxolane ring,” Polymer Degradation and Stability, vol. 75,no. 3, pp. 501–508, 2002.

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

T (K)Slope Intercept

δ2 (J/cm3)1/2

From slope From intercept0,3 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

11International Journal of Polymer Science

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