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Standard molar enthalpy of combustion and formation of quaternary ammonium tetrachlorozincate [n-CnH2n+1 N(CH3)3]2 ZnCl4

  • Biyan Ren1,
  • Shuying Zhang2,
  • Bei Ruan1,
  • Kezhong Wu1Email author and
  • Jianjun Zhang1
SpringerPlus20132:98

https://doi.org/10.1186/2193-1801-2-98

Received: 28 December 2012

Accepted: 28 February 2013

Published: 9 March 2013

Abstract

The standard molar enthalpy of combustion (Δc H o m) and formation (Δf H o m) of quaternary ammonium tetrachlorozincate [n-CnH2n+1N(CH3)3]2ZnCl4 have been determined for the hydrocarbon chain length from even number 8 to 18 of carbon atoms (n) by an oxygen-bomb combustion calorimeter. The results indicated that the values of Δc H o m increased and Δf H o m decreased with increasing chain length and showed a linear dependence on the number of carbon atoms, which were caused by that the order and rigidity of the hydrocarbon chain decreased with increasing the carbon atoms. The linear regression equations are -Δc H o m =1440.50n +3730.67 and -Δf H o m = −85.32n + 1688.22.

Keywords

Combustion calorimeterEnergy of combustionEnthalpy of combustionEnthalpy of formationQuaternary ammonium tetrachlorozincate

Introduction

The quaternary ammonium tetrachlorometallate with the general formula [n- CnH2n+1NR3]2MX4 (M = Cu, Mn, Cd, Zn, Co, …, X = Cl, Br, I, R is alkyl, or aryl) (short notation: CnC3M) have been attracted considerable attention because of their physical properties including ferro-, piezo- or pyroelectricity, ferri-, antiferro- or piezomagnetism and their technical application for electro- or magneto-optical devices (Blachnik et al.1996; Kezhong et al.2010). The advances in synthesis along with the ease of controlling various structural parameters (metal, halogen and number of carbon atoms in the alkylammonium ion) have made them ideal objects for studies by spectroscopy, calorimetry, diffraction, and a variety of other techniques (Abid et al.2011; Donghua et al.2011; Shymkiv et al.2011). In addition, several theoretical studies have been undertaken to predict the behavior of the CnC3M (Francesco et al.2002; Gosniowska et al.2000). However, the thermodynamic properties of the CnC3M have been reported rarely in the literature. In the present work, the series of quaternary ammonium tetrachlorozincate [n-CnH2n+1 N(CH3)3]2ZnCl4 (n = 8, 10, 12, 14, 16, 18) are synthesized from ethanol solutions. The standard molar enthalpy of formation (Δf H o m) and the standard molar enthalpy of combustion (Δc H o m) of the CnC3Zn have been determined by an oxygen-bomb combustion calorimeter with increasing chain length at T = 298.15 K.

Experimental procedure

ZnCl2, concentrated HCl and absolute ethanol were analytical grade. n-Octyltrimethylammonium chloride (A.P.), were purchased from TOKYO CHEMICAL INDUSTRY CO LTD (Japan). n-Decyltrimethylammonium chloride(A.P.), n-Dodecyltrimethylammonium chloride(A.P.), n-Tetradecyltrimethylammonium chloride(A.P.), n-Hexadecyltrimethylammonium chloride(A.P.), n-Trimethylstearylammonium chloride(A.P.) were purchased from J & K CHEMICAL LTD. For the synthesis of CnC3Zn, the hot absolute ethanol solutions of ZnCl2, concentrated HCl and the corresponding quaternary ammonium were mixed in a 1:2:2 molar ratios. The solutions were concentrated by boiling for 1 h, and then cooled to room temperature. After filtration, the products were recrystallized twice from absolute ethanol and then were placed in a vacuum desiccator for 10 h at about 353 K. The CnC3Zn were analyzed with an MT-3 CHN elemental analyzers (Japan) are listed in the following: Elemental analyses calc. (%) for C8C3Zn: C 47.88, H 9.43, N 5.08, Cl 25.75; Found: C 47.45, H 9.50, N 5.13, Cl 24.99. Anal. Calcd for C10C3Zn: C 51.37, H 9.88, N 4.61, Cl 23.38; Found: C 50.98, H 9.95, N 4.58, Cl 22.81. Anal. calcd for C12C3Zn: C 54.26, H 10.25, N 4.22, Cl 21.41; Found: C 53.93, H 10.34, N 4.26, Cl 21.25. Anal. Calcd for C14C3Zn: C 56.72, H 10.56, N 3.89, Cl 19.74; Found: C 56.06, H 10.20, N 3.84, Cl 19.03. Anal. Calcd for C16C3Zn: C 58.84, H 10.84, N 3.61, Cl 18.31; Found: C 58.91, H 10.77, N 3.62,Cl18.72. Anal. Calcd for C18C3Zn: C 60.65, H 11.07, N 3.37, Cl 17.08; Found: C 60.56, H 11.04, N 3.36, Cl 17.55.

The combustion experiments were performed with a static bomb calorimeter (XRY-1A Shanghai). Benzoic acid (Thermochemical Standard, BCS-CRM-190r) was used as calibrant of the bomb calorimeter. Its massic energy of combustion is Δ c U = −(26460 ± 3.8) J · g−1 under certificate conditions. The massic energy of combustion Δc U m for each CnC3Zn was fitted with equation Δc U m = [−ε (calor) · ΔTm ign u ign +V NaOH•(−59.7)]/m CnC3Zn, where ε cal is the energy equivalent of the calorimeter, ΔT is the calorimeter temperature change corrected, Δm ign is the mass of the Nickel-chromium alloy for ignition and the massic energy is u ign  = −3.245 kJ · g−1(U ign = Δm ign u ign ). m CnC3Zn is the mass of the CnC3Zn which were burned, V NaOH is the volume of sodium hydroxid which consumed by nitric acid, the corrections for nitric acid formation were based on −59.7 kJ · mol−1 for the molar energy of formation of 0.1 mol · dm−3 HNO3 (aq) from N2, O2, and H2O(l) (Matos et al.2002). The calibration results were corrected to the average mass of water added to the calorimeter: 2500.0 g and the volume of oxygen bomb was 300 ml. From five independent calibration experiments between T = 295.15 K and T = 299.15 K, the energy equivalent ε cal = (13965.4 ± 4.7) J · K-1 was obtained, where the uncertainty quoted is the standard deviation of the mean. For all experiments, ignition was made at T = (298.150 ± 0.001) K. Combustion experiments were performed in oxygen at a pressure p = 3.00 MPa and in the presence of 10.00 cm3 of water added to the bomb (Matos et al.2002).

Results and discussion

The individual results of all combustion experiments, together with the mean values and their standard deviations, are given for each compound in Table 1. In accordance with normal thermochemical practice, the uncertainties assigned to the standard molar enthalpies of combustion are, in each case, equal to twice the overall standard deviation of the mean and include the uncertainties in calibration (Henoc et al.2009). The results are referred to the following reactions (1 ~ 6) and the following equation (7 ~ 9):
C 8 H 17 N C H 3 3 2 ZnC l 4 s + 69 2 O 2 g = ZnO s + 22 C O 2 g + 4 HCl l + 24 H 2 O l + N 2 g
(1)
C 10 H 21 N C H 3 3 2 ZnC l 4 s + 81 2 O 2 g = ZnO s + 26 C O 2 g + 4 HCl l + 28 H 2 O l + N 2 g
(2)
C 12 H 25 N C H 3 3 2 ZnC l 4 s + 93 2 O 2 g = ZnO s + 30 C O 2 g + 4 HCl l + 32 H 2 O l + N 2 g
(3)
C 14 H 29 N C H 3 3 2 ZnC l 4 s + 105 2 O 2 g = ZnO s + 34 C O 2 g + 4 HCl l + 36 H 2 O l + N 2 g
(4)
C 16 H 33 N C H 3 3 2 ZnC l 4 s + 117 2 O 2 g = ZnO s + 38 C O 2 g + 4 HCl l + 40 H 2 O l + N 2 g
(5)
C 18 H 37 N C H 3 3 2 ZnC l 4 s + 129 2 O 2 g = ZnO s + 42 C O 2 g + 4 HCl l + 44 H 2 O l + N 2 g
(6)
Δ c H o m = c U o m + Δ n RT
(7)
Δ n = n g product n g reactant
(8)
Δ f H o m C n C 3 Zn = ΣV B Δ f H m o B - Δ c H o m
(9)
Table 1

The values of the combustion energies of the quaternary ammonium tetrachlorometallate C n C 3 Zn

 

No.

m CnC3Zn/

Δ T/K

Δmign/g

U ign/J

V NaOH/ml

U NaOH/J

C U m/kJ · g−1

C8C3Zn

1

0.4816

0.950

0.0033

10.71

3.88

23.20

27.478

2

0.5028

0.990

0.0031

10.06

3.78

22.60

27.432

3

0.4725

0.940

0.0041

13.30

4.08

24.40

27.703

4

0.3775

0.750

0.0028

9.09

4.00

23.92

27.658

5

0.5193

1.034

0.0025

8.11

4.40

26.31

27.741

Ave.

27.602 ± 0.139

C10C3Zn

1

0.5081

1.085

0.0041

13.30

2.85

17.04

29.762

2

0.5306

1.120

0.0039

12.66

2.89

17.28

29.422

3

0.5035

1.070

0.0038

12.33

3.39

20.33

29.631

4

0.4403

0.895

0.0030

9.74

2.30

13.75

29.804

5

0.4630

0.950

0.0030

9.74

2.90

17.34

29.640

Ave.

29.652 ± 0.149

C12C3Zn

1

0.4907

1.115

0.0047

15.25

3.03

18.12

31.666

2

0.4591

1.040

0.0049

15.90

2.93

17.54

31.563

3

0.4706

1.060

0.0044

14.28

3.25

19.44

31.385

4

0.4566

1.040

0.0032

10.38

3.20

19.14

31.744

5

0.4673

1.055

0.0040

12.98

3.55

21.23

31.455

Ave.

31.563 ± 0.147

C14C3Zn

1

0.4699

1.120

0.0025

8.11

2.45

14.65

33.238

2

0.5225

1.251

0.0037

12.01

3.65

21.83

33.372

3

0.4130

0.985

0.0039

12.66

2.46

14.71

33.241

4

0.5325

1.270

0.0047

15.25

2.45

14.65

33.251

5

0.4362

1.040

0.0042

13.63

3.75

22.43

33.214

Ave.

33.263 ± 0.062

C16C3Zn

1

0.5125

1.270

0.0046

14.93

2.50

14.97

34.549

2

0.4720

1.160

0.0042

13.63

2.44

14.57

34.262

3

0.4902

1.210

0.0027

8.76

3.04

18.18

34.417

4

0.4758

1.170

0.0043

13.95

3.01

17.99

34.274

5

0.4577

1.130

0.0044

14.28

3.94

23.56

34.396

Ave.

34.379 ± 0.118

C18C3Zn

1

0.5605

1.430

0.0030

9.74

3.04

18.18

35.580

2

0.5755

1.475

0.0058

18.82

3.03

18.12

35.729

3

0.5283

1.348

0.0062

20.12

3.42

20.45

35.557

4

0.4465

1.140

0.0034

11.03

3.65

21.83

35.583

5

0.4459

1.130

0.0038

12.33

3.65

21.83

35.315

Ave.

35.552 ± 0.149

Where R is the molar gas constant and M is the molar mass of the CnC3Zn. The VB is the stoichiometric coefficient and the Δf H o m (B) is the standard molar enthalpy of formation of the combustion products. The standard molar enthalpies of formation of ZnO(s), H2O (l) and CO2(g) at T = 298.15 K, −(348.28) kJ · mol−1, −(285.830 ± 0.042) kJ · mol−1 and − (393.51 ± 0.13) kJ · mol−1 (Manuel et al.2010). The Δf H o m of the CnC3Zn resulted from the Δc H o m by an oxygen-bomb combustion calorimeter at T = 298.15 K. Table 2 lists the values of the standard molar energies Δc U o m, the enthalpies of combustion Δc H o m and the standard molar enthalpies of formation Δf H o m result form Δc U o m for the CnC3Zn.
Table 2

The value of thermochemical functions of the quaternary ammonium tetrachlorometallate C n C 3 Zn

 

C8C3Zn

C10C3Zn

C12C3Zn

C14C3Zn

C16C3Zn

C18C3Zn

c U o m/kJ · mol-1

15268

18010

20938

23929

26657

29557

c H o m/kJ · mol−1

15297

18044

21009

24006

26740

29647

f H o m/kJ · mol−1

991.66

908.02

660.38

380.47

364.10

174.46

The influence of the hydrocarbon chain length on Δc H o m and Δf H o m of the CnC3Zn has been obtained for chain lengths from 8 to 18 carbon atoms. The values of Δc H o m and Δf H o m show a linear dependence on the number of carbon atoms from experimental data analysis. Figure 1, Figure 2 show a plot of the calculated -Δc H o m and -Δf H o m vs. C-atoms (n) that gave a straight line relationship from the values of Table 2. The linear regression equation are -Δc H o m =1440.50n +3730.67 with a correlation coefficient r = 0.9998 and - Δf H o m = −85.32n + 1688.22 with r =0.9512. A striking feature is that Δc H o m increased and Δf H o m decreased with increasing the chain length. This reason is that the structures of CnC3Zn are characteristic of the piling of sandwiches in which a two-dimensional cavities of ZnCl4 2- tetrahedra is sandwiched between two alkylammonium layers. The layers are bound by van der Waals forces between (CH2)nCH3 groups and by long-range Coulomb forces. The –N(CH)3 3+ groups of the chains occupy the cavities of the ZnCl4 2- layers and are bonded by ion bonds to the chlorine atoms (Weizhen et al.2011). As the hydrocarbon chain length increases, the formation of the chain conformer plays a more important role in the structural phase transitions. It is known that the order and rigidity of the hydrocarbon chain were decreased with increasing the carbon atoms, that is with increasing mean number of conformationally flexible chain in CnC3Zn (Nobuaki et al.2011), furthermore, the intensities of the ion bonds and van der Walls force decrease with increasing the carbon atoms resulting in that the values of Δc H o m and Δf H o m show a linear dependence on the carbon atoms.
Figure 1

Plot of Δ c H o m vs. number( n ) of carbon-atoms in the quaternary ammonium tetrachlorometallate C n C 3 Zn.

Figure 2

Plot of Δ f H o m vs. number( n ) of carbon-atoms in the quaternary ammonium tetrachlorometallate C n C 3 Zn.

Conclusions

The standard molar enthalpy of combustion and formation of quaternary ammonium tetrachlorozincate [n-CnH2n+1 N(CH3)3]2ZnCl4 (n = 8, 10, 12, 14, 16, 18) have been measured by an oxygen-bomb combustion calorimeter. The results indicated that the values of the standard molar combustion enthalpies Δc H o m of these compounds increased with increasing chain length and the standard molar formation enthalpies Δf H o m of these compounds decreased with increasing chain length and showed a linear dependence on the number of carbon atoms.

Declarations

Acknowledgements

This project was financially supported by National Natural Science Foundation of China (No.21073052, 21246006), Natural Science Foundation of Hebei Province (No. B2012205034), and Science Foundation of Hebei Normal University (L2011K04).

Authors’ Affiliations

(1)
Department of Chemistry and Material Science, Hebei Normal University
(2)
Department of Basic Course, the Chinese People’s Armed Police Force Academy

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© Ren et al.; licensee Springer. 2013

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