5. ENTHALPY CHANGES FOR BINARY COPOLYMER SOLUTIONS 5.1. Enthalpies of mixing or intermediary enthalpies of dilution, and copolymer partial enthalpies of mixing (at infinite dilution), or copolymer (first) integral enthalpies of solution _____________________________________________________________________________ Copolymers from acrylonitrile and butadiene _____________________________________________________________________________ Average chemical composition of the copolymers, acronyms and references: _____________________________________________________________________________ Copolymer (B) Acronym Ref. _____________________________________________________________________________ Acrylonitrile/butadiene copolymer 18.0 wt% acrylonitrile AN-B/18w 55TA1 26.0 wt% acrylonitrile AN-B/26w(1) 50TAG 26.0 wt% acrylonitrile AN-B/26w(1) 51TAG 26.0 wt% acrylonitrile AN-B/26w(2) 55TA1 40.0 wt% acrylonitrile AN-B/40w(1) 50TAG 40.0 wt% acrylonitrile AN-B/40w(1) 51TAG 40.0 wt% acrylonitrile AN-B/40w(2) 55TA1 _____________________________________________________________________________ Characterization: _____________________________________________________________________________ Copolymer (B) M n / M w / M η / Further information g/mol g/mol g/mol _____________________________________________________________________________ AN-B/18w no data AN-B/26w(1) Buna No. 26 AN-B/26w(2) no data AN-B/40w(1) Buna No. 40 AN-B/40w(2) no data _____________________________________________________________________________ © 2001 by CRC Press LLC Experimental enthalpy data: _____________________________________________________________________________ copolymer (B): AN-B/18w 55TA1 solvent (A): benzene C 6 H 6 71-43-2 T/K = 298.15 ∆ sol H B ∞ = 0.0 J/(g copolymer) Comments: the final concentration is about 2 g copolymer/132 g solvent copolymer (B): AN-B/26w(1) 50TAG, 51TAG solvent (A): benzene C 6 H 6 71-43-2 T/K = 298.15 ∆ sol H B ∞ = 5.82 J/(g copolymer) Comments: the final concentration is about 0.55 g copolymer/100 g solution copolymer (B): AN-B/26w(2) 55TA1 solvent (A): benzene C 6 H 6 71-43-2 T/K = 298.15 ∆ sol H B ∞ = −1.88 J/(g copolymer) Comments: the final concentration is about 3 g copolymer/132 g solvent copolymer (B): AN-B/40w(1) 50TAG, 51TAG solvent (A): benzene C 6 H 6 71-43-2 T/K = 298.15 ∆ sol H B ∞ = −7.0 J/(g copolymer) Comments: the final concentration is about 0.85 g copolymer/100 g solution copolymer (B): AN-B/40w(2) 55TA1 solvent (A): benzene C 6 H 6 71-43-2 T/K = 298.15 ∆ sol H B ∞ = −2.93 J/(g copolymer) Comments: the final concentration is about 3 g copolymer/88 g solvent © 2001 by CRC Press LLC _____________________________________________________________________________ Copolymers from acrylonitrile and isoprene _____________________________________________________________________________ Average chemical composition of the copolymers, acronyms and references: _____________________________________________________________________________ Copolymer (B) Acronym Ref. _____________________________________________________________________________ Acrylonitrile/isoprene copolymer 85.0 mol% acrylonitrile AN-IP/85x 76PET _____________________________________________________________________________ Characterization: _____________________________________________________________________________ Copolymer (B) M n / M w / M η / Further information g/mol g/mol g/mol _____________________________________________________________________________ AN-IP/85x no data _____________________________________________________________________________ Experimental enthalpy data: _____________________________________________________________________________ copolymer (B): AN-IP/85x 76PET solvent (A): N,N-dimethylformamide C 3 H 7 NO 68-12-2 T/K = 323.15 ∆ sol H B ∞ = −31.8 J/(g copolymer) Comments: additional information is given for varying isoprene contents between 2 and 22 mol% in the copolymer in Fig. 1 of the original source 76PET © 2001 by CRC Press LLC _____________________________________________________________________________ Copolymers from acrylonitrile and vinyl chloride _____________________________________________________________________________ Average chemical composition of the copolymers, acronyms and references: _____________________________________________________________________________ Copolymer (B) Acronym Ref. _____________________________________________________________________________ Acrylonitrile/vinyl chloride copolymer 13.0 wt% acrylonitrile AN-VC/13w 59ZEL 29.0 wt% acrylonitrile AN-VC/29w 59ZEL 40.0 wt% acrylonitrile AN-VC/40w 59ZEL _____________________________________________________________________________ Characterization: _____________________________________________________________________________ Copolymer (B) M n / M w / M η / Further information g/mol g/mol g/mol _____________________________________________________________________________ AN-VC/13w no data AN-VC/29w no data AN-VC/40w no data _____________________________________________________________________________ Experimental enthalpy data: _____________________________________________________________________________ copolymer (B): AN-VC/13w 59ZEL solvent (A): N,N-dimethylformamide C 3 H 7 NO 68-12-2 T/K 295.15 308.15 308.15 323.15 323.15 338.15 338.15 ∆ sol H B ∞ /(g copolymer) −37.95 −22.18 −21.34 −19.25 −16.95 −15.48 −14.64 T/K 353.15 353.15 ∆ sol H B ∞ /(g copolymer) −12.97 −11.30 Comments: the final concentration is about 1 g copolymer/165 g solvent © 2001 by CRC Press LLC copolymer (B): AN-VC/29w 59ZEL solvent (A): N,N-dimethylformamide C 3 H 7 NO 68-12-2 T/K 295.15 295.15 308.15 308.15 323.15 323.15 338.15 ∆ sol H B ∞ /(g copolymer) −43.93 −40.21 −27.61 −26.78 −22.18 −20.08 −20.50 T/K 338.15 353.15 353.15 ∆ sol H B ∞ /(g copolymer) −17.99 −16.32 −15.90 Comments: the final concentration is about 1 g copolymer/165 g solvent copolymer (B): AN-VC/40w 59ZEL solvent (A): N,N-dimethylformamide C 3 H 7 NO 68-12-2 T/K 295.15 295.15 308.15 323.15 323.15 338.15 338.15 ∆ sol H B ∞ /(g copolymer) −47.28 −46.65 −30.54 −28.87 −26.36 −20.08 −19.66 T/K 353.15 ∆ sol H B ∞ /(g copolymer) −17.15 Comments: the final concentration is about 1 g copolymer/165 g solvent _____________________________________________________________________________ Copolymers from acrylonitrile and vinylidene chloride _____________________________________________________________________________ Average chemical composition of the copolymers, acronyms and references: _____________________________________________________________________________ Copolymer (B) Acronym Ref. _____________________________________________________________________________ Acrylonitrile/vinylidene chloride copolymer unspecified contents of acrylonitrile AN-VdC/? 55ZAZ _____________________________________________________________________________ Characterization: _____________________________________________________________________________ Copolymer (B) M n / M w / M η / Further information g/mol g/mol g/mol _____________________________________________________________________________ AN-VdC/? fibre "Saniv", USSR _____________________________________________________________________________ © 2001 by CRC Press LLC Experimental enthalpy data: _____________________________________________________________________________ copolymer (B): AN-VdC/? 55ZAZ solvent (A): 2-propanone C 3 H 6 O 67-64-1 T/K = 298.15 ∆ sol H B ∞ = −28.03 J/g copolymer T/K = 298.15 ∆ sol H B ∞ = −19.25 J/g copolymer (fibre drawn 156%) T/K = 298.15 ∆ sol H B ∞ = −15.92 J/g copolymer (fibre drawn 300%) T/K = 298.15 ∆ sol H B ∞ = −14.23 J/g copolymer (fibre drawn 400%) _____________________________________________________________________________ Copolymers from bisphenol A-isophthaloyl chloride and terephthaloyl chloride _____________________________________________________________________________ Average chemical composition of the copolymers, acronyms and references: _____________________________________________________________________________ Copolymer (B) Acronym Ref. _____________________________________________________________________________ Bisphenol A-isophthaloyl chloride/terephthaloyl chloride copolymer 50 mol% terephthaloyl chloride BAIPC-TPC/50x 78SOK _____________________________________________________________________________ Characterization: _____________________________________________________________________________ Copolymer (B) M n / M w / M η / Further information g/mol g/mol g/mol _____________________________________________________________________________ BAIPC-TPC/50x synthesized in the laboratory _____________________________________________________________________________ © 2001 by CRC Press LLC Experimental enthalpy data: _____________________________________________________________________________ copolymer (B): BAIPC-TPC/50x 78SOK solvent (A): N,N-dimethylacetamide C 4 H 9 NO 127-19-5 T/K = 298.15 ∆ sol H B ∞ = −56.5 J/(g copolymer) Comments: amorphous sample copolymer (B): BAIPC-TPC/50x 78SOK solvent (A): 1,1,2,2-tetrachloroethane C 2 H 2 Cl 4 79-34-5 T/K = 298.15 ∆ sol H B ∞ = 72.5 J/(g copolymer) Comments: amorphous sample copolymer (B): BAIPC-TPC/50x 78SOK solvent (A): 1,1,2,2-tetrachloroethane C 2 H 2 Cl 4 79-34-5 T/K = 298.15 ∆ sol H B ∞ = 41.9 J/(g copolymer) Comments: partially crystalline sample _____________________________________________________________________________ Copolymers from butadiene and styrene _____________________________________________________________________________ Average chemical composition of the copolymers, acronyms and references: _____________________________________________________________________________ Copolymer (B) Acronym Ref. _____________________________________________________________________________ Butadiene/styrene copolymer 10.0 wt% styrene S-BR/10w 55TA2 10.0 wt% styrene S-BR/10w 58TA2 30.0 wt% styrene S-BR/30w(1) 55TA2 30.0 wt% styrene S-BR/30w(1) 58TA2 _____________________________________________________________________________ continue © 2001 by CRC Press LLC continue _____________________________________________________________________________ Copolymer (B) Acronym Ref. _____________________________________________________________________________ Butadiene/styrene copolymer 30.0 wt% styrene S-BR/30w(2) 56STR 30.0 wt% styrene S-BR/30w(2) 58SLO 50.0 wt% styrene S-BR/50w 55TA2 50.0 wt% styrene S-BR/50w 58TA2 60.0 wt% styrene S-BR/60w 55TA2 60.0 wt% styrene S-BR/60w 58TA2 70.0 wt% styrene S-BR/70w 55TA2 70.0 wt% styrene S-BR/70w 58TA2 75.0 wt% styrene S-BR/75w 50TAG 75.0 wt% styrene S-BR/75w 51TAG 80.0 wt% styrene S-BR/80w 55TA2 80.0 wt% styrene S-BR/80w 58TA2 90.0 wt% styrene S-BR/90w 55TA2 90.0 wt% styrene S-BR/90w 58TA2 _____________________________________________________________________________ Characterization: _____________________________________________________________________________ Copolymer (B) M n / M w / M η / Further information g/mol g/mol g/mol _____________________________________________________________________________ S-BR/10w synthesized in the laboratory S-BR/30w(1) synthesized in the laboratory S-BR/30w(2) intrinsic viscosity = 1.50 S-BR/50w synthesized in the laboratory S-BR/60w synthesized in the laboratory S-BR/70w synthesized in the laboratory S-BR/75w Buna-S S-BR/80w synthesized in the laboratory S-BR/90w synthesized in the laboratory _____________________________________________________________________________ Experimental enthalpy data: _____________________________________________________________________________ copolymer (B): S-BR/10w 55TA2 solvent (A): benzene C 6 H 6 71-43-2 T/K = 293.65 w B 0.1 0.2 0.3 0.4 0.5 0.7 0.8 0.99 ∆ M H/(J/g) 0.33 0.63 0.92 1.26 1.59 2.43 2.55 0.42 © 2001 by CRC Press LLC copolymer (B): S-BR/10w 55TA2 solvent (A): benzene C 6 H 6 71-43-2 T/K = 293.65 ∆ sol H B ∞ = 4.94 J/(g copolymer) Comments: the final concentration is about 2.7 g copolymer/100 ml solvent copolymer (B): S-BR/10w 55TA2 solvent (A): ethylbenzene C 8 H 10 100-41-4 solvent (C): 2,2,4-trimethylpentane C 8 H 18 540-84-1 T/K = 298.15 ∆ sol H B ∞ = 1.46 J/(g copolymer) Comments : solvent mixture concentration 10 wt% C 8 H 10 / 90 wt% C 8 H 18 copolymer (B): S-BR/30w(1) 55TA2 solvent (A): benzene C 6 H 6 71-43-2 T/K = 293.65 w B 0.1 0.2 0.3 0.4 0.5 0.685 0.943 0.96 ∆ M H/(J/g) 0.17 0.38 0.54 0.71 0.88 1.21 0.92 0.67 copolymer (B): S-BR/30w(1) 55TA2 solvent (A): benzene C 6 H 6 71-43-2 T/K = 293.65 ∆ sol H B ∞ = 3.01 J/(g copolymer) Comments: the final concentration is about 2.7 g copolymer/100 ml solvent copolymer (B): S-BR/30w(2) 56STR, 58SLO solvent (A): benzene C 6 H 6 71-43-2 T/K = 298.15 ∆ sol H B ∞ = 3.05 J/(g copolymer) Comments: final concentration 1 g copolymer/100 g solvent © 2001 by CRC Press LLC copolymer (B): S-BR/30w(1) 55TA2 solvent (A): ethylbenzene C 8 H 10 100-41-4 solvent (C): 2,2,4-trimethylpentane C 8 H 18 540-84-1 T/K = 298.15 ∆ sol H B ∞ = 0.75 J/(g copolymer) Comments : solvent mixture concentration 30 wt% C 8 H 10 / 70 wt% C 8 H 18 copolymer (B): S-BR/50w 55TA2 solvent (A): benzene C 6 H 6 71-43-2 T/K = 293.65 ∆ sol H B ∞ = 1.80 J/(g copolymer) Comments: the final concentration is about 4 g copolymer/100 ml solvent copolymer (B): S-BR/50w 55TA2 solvent (A): ethylbenzene C 8 H 10 100-41-4 solvent (C): 2,2,4-trimethylpentane C 8 H 18 540-84-1 T/K = 298.15 ∆ sol H B ∞ = 0.54 J/(g copolymer) Comments : solvent mixture concentration 50 wt% C 8 H 10 / 50 wt% C 8 H 18 copolymer (B): S-BR/60w 55TA2 solvent (A): benzene C 6 H 6 71-43-2 T/K = 293.65 w B 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 ∆ M H/(J/g) 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 copolymer (B): S-BR/60w 55TA2 solvent (A): benzene C 6 H 6 71-43-2 T/K = 293.65 ∆ sol H B ∞ = 0.0 J/(g copolymer) Comments: the final concentration is about 4 g copolymer/100 ml solvent © 2001 by CRC Press LLC [...]... 95KIL 56- 23-5 CCl4 T/K = 303.15 wB 0.00 76 0.0147 ∆MH/(J/g) −0. 067 −0.134 0.0251 −0.2 36 0.0353 −0.340 0.0453 −0.443 0.0551 −0.5 46 0. 065 8 −0 .66 3 0.0 763 −0.7 76 0.0 866 −0.889 wB 0.0 966 0.1 064 ∆MH/(J/g) −0.998 −1.104 0.1 160 −1.209 0.1 265 −1.321 0.1 368 −1.429 0.1 564 −1 .61 2 0. 168 7 −1.718 0.18 06 −1.822 0.1935 −1.932 wB 0.2059 0.2180 ∆MH/(J/g) −2.037 −2.139 0.2297 −2.235 0.2411 −2.327 0.2 567 −2.425 0.2852 −2 .65 3... small heat of fusion of this copolymer copolymer (B): solvent (A): E-P/33x 2,2,4 ,6, 6-pentamethylheptane C12H 26 79PH1, 79PH2 13475-82 -6 C12H 26 79PH1, 79PH2 13475-82 -6 C12H 26 79PH1, 79PH2 13475-82 -6 T/K = 298.15 ∆MHB∞ = −0.3 J/(g copolymer) copolymer (B): solvent (A): E-P /63 x 2,2,4 ,6, 6-pentamethylheptane T/K = 298.15 ∆MHB∞ = +3 .6 J/(g copolymer) copolymer (B): solvent (A): E-P/75x 2,2,4 ,6, 6-pentamethylheptane... the copolymer in the starting solution and ϕB(2) denotes the volume fraction after the dilution process copolymer (B): solvent (A): S-BMA/80w 2-butanone 87KYO 78-93-3 C4H8O T/K = 298.15 ϕB(1) ϕB(2) ∆dilH12/(J/mol) 0.0 465 0.0189 0.104 0.0 465 0.0279 0. 164 0.0 465 0.03 26 0.121 ϕB(1) ϕB(2) ∆dilH12/(J/mol) 0.0 766 0.0543 0.555 0.0 766 0. 062 1 0.7 06 0.0 766 0. 069 8 0. 867 Comments: 0.0 465 0.0372 0.228 0.0 465 0.0419... −0 .61 8 0. 062 8 −0.925 0.0838 −1.205 0.1235 −1 .68 5 0. 160 2 −2.0 96 0.1942 −2.437 0.2370 −2.8 56 0.2402 −2.897 wB 0.2 763 0.29 36 ∆MH/(J/g) −3.178 −3.287 0.3121 −3.4 36 0.3449 −3.578 0.3804 −3.728 0.4241 −3.844 0.4792 −3.902 0.53 06 −3. 860 0.5942 −3 .69 0 wB 0 .67 51 0.72 46 ∆MH/(J/g) −3.324 −3.010 0.7818 −2. 564 0.8487 −1.917 0.9283 −0.950 0.9739 −0.298 0.9935 −0.078 copolymer (B): solvent (A): EO-PO-EO /61 x tetrachloromethane... (A): E-P /63 x 2,2,4,4 ,6, 8,8-heptamethylnonane T/K = 298.15 ∆MHB∞ = +2.2 J/(g copolymer) copolymer (B): solvent (A): E-P/75x 2,2,4,4 ,6, 8,8-heptamethylnonane T/K = 298.15 ∆MHB∞ = −0.9 J/(g copolymer) © 2001 by CRC Press LLC copolymer (B): solvent (A): E-P/33x n-hexadecane C16H34 79PH1, 79PH2 544- 76- 3 C16H34 79PH1, 79PH2 544- 76- 3 C16H34 79PH1, 79PH2 544- 76- 3 T/K = 298.15 ∆MHB∞ = +0.7 J/(g copolymer) copolymer. .. E-P /63 x n-hexadecane T/K = 298.15 ∆MHB∞ = −1.1 J/(g copolymer) copolymer (B): solvent (A): E-P/75x n-hexadecane T/K = 298.15 ∆MHB∞ = −4 .6 J/(g copolymer) Comments: after subtracting the small heat of fusion of this copolymer copolymer (B): solvent (A): E-P /63 x 3-methylhexane C7H 16 79PH1, 79PH2 589-34-4 C7H 16 79PH1, 79PH2 589-34-4 C8H18 79PH1, 79PH2 111 -65 -9 T/K = 298.15 ∆MHB∞ = +0.7 J/(g copolymer) copolymer. .. (A): E-P /63 x 2,3-dimethylpentane T/K = 298.15 ∆MHB∞ = +0.7 J/(g copolymer) © 2001 by CRC Press LLC copolymer (B): solvent (A): E-P/75x 2,3-dimethylpentane C7H 16 79PH1, 79PH2 565 -59-3 C7H 16 79PH1, 79PH2 108-08-7 C7H 16 79PH1, 79PH2 108-08-7 C7H 16 79PH1, 79PH2 108-08-7 C7H 16 79PH1, 79PH2 562 -49-2 C7H 16 79PH1, 79PH2 562 -49-2 C12H 26 79PH1, 79PH2 112-40-3 T/K = 298.15 ∆MHB∞ = +0.4 J/(g copolymer) copolymer. .. 58TA1 67 -64 -1 C4H8O2 C2H6O 58TA1 141-78 -6 64-17-5 T/K = 298.15 ∆solHB∞ = 0.0 J/(g copolymer) copolymer (B): solvent (A): solvent (C): VA-VAL /67 w ethyl acetate ethanol T/K = 298.15 ∆solHB∞ = 0.0 J/(g copolymer) Comments: the solvent mixture concentration is equal to the comonomer contents, i.e., 67 .0 wt% ethyl acetate/33.0 wt% ethanol copolymer (B): solvent (A): VA-VAL /67 w 2-propanone C3H6O 58TA1 67 -64 -1... −0. 065 0.0215 −0.1 36 0.03 16 −0.209 0.0449 −0.309 0.0577 −0.407 0.0850 −0 .62 4 0.1107 −0.837 0.1339 −0. 967 wB 0.1573 0.19 36 ∆MH/(J/g) −1.123 −1.331 0.2284 −1.503 0.2729 −1 .69 4 0.3432 −1.924 0.4134 −2.094 0.4892 −2.138 0.5528 −2.158 0 .61 62 −2.045 wB 0.7140 0.8178 ∆MH/(J/g) −1.817 −1.455 0.90 76 −0.829 0.9389 −0. 566 0.9723 −0.254 copolymer (B): solvent (A): EO-PO-EO/91x tetrachloromethane 85COR, 95KIL 56- 23-5... −0. 361 0. 061 3 −0. 564 0.08 96 −0.834 0.1207 −1.130 0.1498 −1.394 0.1770 −1 .61 7 0.2272 −2.048 wB 0.27 26 0.3285 ∆MH/(J/g) −2. 367 −2 .66 8 0.3974 −2.907 0.4479 −2.999 0.5449 −2.945 0 .66 77 −2.535 0.7389 −2.130 0.8270 −1.4 96 0.9053 −0.837 _ Copolymers from isobutyl methacrylate and methyl methacrylate _ Average chemical composition of . CHANGES FOR BINARY COPOLYMER SOLUTIONS 5.1. Enthalpies of mixing or intermediary enthalpies of dilution, and copolymer partial enthalpies of mixing (at infinite dilution), or copolymer (first). 0.4 0.5 0 .68 5 0.943 0. 96 ∆ M H/(J/g) 0.17 0.38 0.54 0.71 0.88 1.21 0.92 0 .67 copolymer (B): S-BR/30w(1) 55TA2 solvent (A): benzene C 6 H 6 71-43-2 T/K = 293 .65 ∆ sol H B ∞ = 3.01 J/(g copolymer) Comments:. C 7 H 16 562 -49-2 T/K = 298.15 ∆ M H B ∞ = −2.7 J/(g copolymer) copolymer (B): E-P /63 x 79PH1, 79PH2 solvent (A): 3,3-dimethylpentane C 7 H 16 562 -49-2 T/K = 298.15 ∆ M H B ∞ = +0.3 J/(g copolymer) copolymer