Thermochemical Parameters of 3-Chloroaniline Complexes of Certain Bivalent Transition Metal Bromides

doi:10.4236/ojpc.2013.34020

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Open Journal of Physical Chemistry, 2013, 3, 163-169

Published Online November 2013 (http://www.scirp.org/journal/ojpc)

http://dx.doi.org/10.4236/ojpc.2013.34020

Open Access OJPC

Thermochemical Parameters of 3-Chloroaniline Complexes

of Certain Bivalent Transition Metal Bromides

Pedro Oliver Dunstan*, Abdul Majeed Khan

Instituto de Química, Universidade Estadual de Campinas, Campinas, Brazil

Email: *[email protected]

Received August 13, 2013; revised September 10, 2013; accepted September 18, 2013

mons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work

is properly cited.

ABSTRACT

Complexes of general formula [MBr2(3-clan)n] (where M is Fe, Ni, Cu or Zn; 3-clan = m-chloroaniline; n is 1.5 or 2)

were prepared and their characteristic properties, such as capillary MP; C, H, N, Br and metal contents; TG/DTG and

DSC curves; and IR and electronic spectra were determined. By calorimetric measurements in solution, the values of

some thermodynamic parameters of the complexes were determined. From these values, the standard enthalpies of the

metal-nitrogen coordinated bonds were calculated, and the standard enthalpies of the formation of the gaseous phase

complexes were estimated.

Keywords: Enthalpies of Formation; Thermodynamic; Coordinated Bond Enthalpies; Calorimetric Measurements

1. Introduction

The standard enthalpies of formation are fundamental

characteristics of complexes. Thermodynamic data in the

literature concerning the standard enthalpies of formation

of coordinated bonds in complexes are limited. Additional

compounds that divalent transition metal salts form with

the aniline ligand and its derivatives are mentioned in the

literature [1-26]. In a previous article [11], complexes

formed by 4-chloroaniline with several divalent transi-

tion metal bromides were studied. In this work, the com-

plexes formed by 3-chloroaniline with bromides of

iron(II), nickel(II), cooper(II) and zinc(II) were studied.

The thermodynamic characterization of these compounds

is important because the finding concerning thermody-

namic properties can be used to determine their applica-

tions in catalyses and in chromatographic separation of

metal ions. Calorimetric measurements were performed

to measure the strength of the metal-nitrogen coordinated

bonds. Several correlations of the thermodynamic pa-

rameters published in the literature for aniline and

4-chloroaniline complexes with the parameters of the

3-chloroaniline complexes prepared in this study were

also obtained. It is expected that the ligand 4-chloroani-

line forms a weaker coordinated bond than 3-chloro-

anilne due to the inductive effect of the electron with-

drawing chloro atom in the phenyl ring. The effect is

stronger in the para-position than that in the meta-posi-

tion. Aniline must form the stronger bond, because it

does not have any substitution in the phenyl ring. The

enthalpy of formation of the complexes derived from the

gaseous-phase metal ions, bromide ions and 3-chloro-

aniline has been determined.

2. Materials and Methods

2.1. Reagents

The purity of 3-chloroaniline (98%, Aldrich) was im-

proved by the method of Riddick [27]. The anhydrous

metal dibromides used in the synthesis were of analytical

grade. Solvents were distilled and stocking over Linde 4

Å molecular sieves before using.

2.2. Experimental Procedure

Complexes were obtained by reacting the metal

dibromides and 3-chloroaniline in solution. Hot ethanol

was used as a solvent with a molar ratio salt/ligand of 1/4.

The following is an example of the preparations: 1.10 g

of NiBr2 (5.03 × 10−3 mol) was dissolved in 20 mL of hot

ethanol (343 K), and 2.57 g (2.13 mL, 20.13 × 10−3 mol)

of 3-chloroaniline was poured into the solution of the salt,

slowly and dropwise. The stirring was maintained after

*Corresponding author.

P. O. DUNSTAN, A. M. KHAN

164

the complete addition of the ligand. A green solid was

formed which was filtered and washed with 60 mL of

petroleum ether divided in three portions. The compound

obtained was maintained in a vacuum over several hours.

It was stocked in a desiccator over CaCl2. The chemical

analysis confirmed the contents proposed by the assumed

stoichiometries. Microanalytical procedures [28] were

used for the determination of C, H and N contents. The

bromine contents were determined by gravimetric analy-

sis [29]. The metal contents were complexometrically

determined using 0.01 M ethylenediaminetetraacetic acid

solution [30]. Samples of the compounds in a KBr matrix

were used to obtain the IR spectra. For the ligand, a film

of it between KBr plates was used. The region was from

4000 to 400 cm−1 and a Perkin Elmer 1600 series FTIR

Spectrophotometer was used. A UV-Vis-NIR Varian-

Cary SG spectrophotometer was used to record the spec-

tra of the compounds in the region of 350 - 2000 nm us-

ing a standard reflectance attachment to obtain the spec-

tra of the solid compounds. TG/DTG and DSC curves

were recorded in an argon atmosphere in a Du Pont 951

analyzer. The mass of the samples was initially between

6.37 and 8.79 mg (TG/DTG) and from 2.65 to 4.47 mg

(DSC). A heating rate of 10 K·min−1 was used from 298

to 678 K (DSC) and from 298 to 1248 K (TG/DTG). The

calibration for temperatures was made with metallic alu-

minum as a standard (mp 933.49 K). The equipment

performed the calibration for mass automatically. The

DSC calibration was conducted with metallic indium as a

standard (mp = 438.85 K, ). For the

calorimetric study of the compounds, an LKB 8700-1

precision calorimeter was used. The temperature of the

measurements was 298.15  0.02 K. A thin-walled am-

poule that contained reactant was broken in a glass reac-

tion vessel filled with (100.00 mL) of calorimetric sol-

vent [31]. The accuracy of the equipment was determined

as previously reported [31,32]. Three to six replicate

measurements were made on each compound and the

uncertainty intervals are twice the standard deviations.

The experimental deviations of the dissolution measure-

ments were between (0.7% - 2.8%).

lo 1

s28.4 JgH

 

3. Results

3.1. Complex Characterization

All complexes were solids. The interaction of MnBr2 and

CoBr2 with 3-chloroaniline did not lead to the formation

of compounds with a definite stoichiometry. The out-

comes of the synthesis, capillary mp, colors, appearance,

and elemental contents are presented in Table 1.

3.2. Infrared Spectra

Some absorption bands of the compounds are presented

in Table 2. The band attributed to the stretching vibra-

tion of the NH group ((N-H)) in the free ligand is shifted

towards lower frequencies in the coordinated ligand. This

is observed when aniline and aniline derivatives coordi-

nates to the metal ions [33,34]. Figure 1 presents the IR

spectra of the Cu(II) adduct.

3.3. Thermal Studies

The (TG/DTG) curves of the Cu and Zn complexes

showed the elimination of all the ligand in three steps of

mass loss, with the elimination of all the bromine content

together with part of the metal content in the third stage

of mass loss. The curve of the complex of Fe showed the

mass of the ligand being eliminated in three stages with

part of the bromine content being eliminated in the third

stage together with part of the ligand content followed by

the elimination of part of the bromine content in a fourth

stage of mass loss. The curve of the complex of Ni

showed the elimination of all the ligand in two stages

with the elimination of part of the bromine content in a

third stage of mass loss. The TG/DTG curves showed a

residue that is the metal content plus part of the bromine

content for the complexes of Fe and Ni. This residue is

part of the metal content for the complexes of Cu and Zn.

Figure 2 presents the TG/DTG curve of the Ni(II) com-

plex. The DSC curves of the complexes show endother-

mic peaks that are consistent with the elimination of part

of the ligand. Figure 3 presents the DSC curve of the

Table 1. Melting points, yields, appearance and analytical data* of the complexes.

COMPOUND YIELD MPA APPEAR.B %C %H %N %Br %M

K Calc. Found Calc. Found Calc. Found Calc. Found Calc. Found

[FeBr2(3-lan)1.5] 17 500-3 b.p. 26.53 26.28

(−0.94) 2.23 2.43

(8.97) 5.16 5.88

(13.95)39.26 38.84

(−1.07) 13.72 13.33

(−2.84)

[NiBr2(3-clan)1.5] 64 392-5 l.g.p. 26.3526.81

(1.75) 2.21 2.58

(16.74) 5.12 5.19

(1.37)38.99 38.20

(−2.03) 14.32 13.93

(−2.72)

[CuBr2(3-clan)2] 56 446-500 d.b. p. 30.09 29.54

(−1.83) 2.52 2.13

(−15.48) 5.85 5.49

(−6.15) 35.77 35.13

(−0.18) 13.28 12.98

(−2.26)

[ZnBr2(3-clan)2] 84 387-90 w.p. 29.9730.04

(0.23) 2.51 2.37

(−5.58)5.82 5.72

(−1.72) 33.26 33.78

(1.56) 13.61 13.40

(−1.54)

Melting with decomposition. BKey: b., brown; g., green; w., white; l., light; d., dark; p., powder. *(Standard deviation errors, %).

Open Access OJPC

P. O. DUNSTAN, A. M. KHAN 165

Table 2. Main IR spectral data (cm−1) of the complexes.

Compound



(N-H)



(N-H)

3-clan 3444 m, 3362 m 1602 s, 1597 s

[FeBr2(3-clan)1.5] 3430 s, 2875 s, 2825 s 1596 m, 1564 m

[NiBr2(3-clan)1.5] 3405 s, 3329 s 1602 s, 1578 m

CuBr2(3-clan)2] 3434 m, 3291 s, 3231 s 1592 s, 1560 m

ZnBr2(3-clan)2] 3436 m, 3263 s, 3215 s 1598 s, 1573 m

Key:



, stretching;



, angular deformation. Intensity of bands: s, strong; m.

medium.

Figure 1. Infrared spectrum of the complex [CuBr2(3-clan)2].

Figure 2. TG/DTG curve of the complex [NiBr2(3-clan)1.5].

Ni(II) complex. Table 3 shows the thermal data obtained

for the complexes. Discrepancies between the calculated

and observed mass losses are due to losses through the

TG curve between one step and the following step of

mass loss.

3.4. Electronic Spectra

The complex of Ni showed the metal ions in the center of

pseudo-octahedral units [NiL2Br4]2− and [NiLBr5]3−

forming a three-dimensional polymer. This was con-

Figure 3. DSC curve of the complex [NiBr2(3-clan)1.5].

cluded from the values of the calculated ligand field pa-

rameters and the positions of the absorption bands

[35,36]. The complex of Fe showed the metal ions in the

center of pseudo-octahedral units [FeL2Br4]2− and

[FeLBr5]3− forming a three-dimensional polymer. This

was concluded from the values of the calculated ligand

field parameter and position of the absorption band [37].

The Cu complex showed the metal ion in the center of

pseudo-tetrahedrons [CuL2Br2]. This was concluded from

the appearance and position of the broth absorption band

at (15,862 cm−1) [37]. Table 4 presents the attribution of

the absorption bands and the calculated values of the

ligand field parameters for the compounds.

3.5. Calorimetric Measurements

The solution enthalpy measurements of the compounds

were made accordingly to the following reactions [38]:



MBrselected solventsolution a;

 (1)







n3-clansolution asolution b;

  (2)







2ns

MBr3-clanselected solvent

solution c;H









(3)

solution bsolution c;

 (4)

According to Hess’law for the reactions (1)-(4), the

standard enthalpy of reaction (rH



) of the following

reaction:

 







2s lns

MBrn 3-clanMBr3-clan;









(5)

is equal to: ooo

r123

HHH, because the

final state of reactions (2) and (3) is the same and 4H



0, and also because the dilution of solution b into solu-

tion c has no thermal effect. Table 5 presents the values

Open Access OJPC

P. O. DUNSTAN, A. M. KHAN

166

Table 3. Thermal analysis of the compounds.

Compound App. MP/K mass loss(%) TG temp. range/KSpecies lost DSC p. temp. Ho

Calcd. Obs.b

kJ·mol−1

[FeBr2(3-clan)1.5] 500 - 503 28.20 28.98(6.31%) 361 - 409 −0.9L 386 39.13

10.97 11.07(0.91%) 409 - 534 −0.35L 398 17.96

23.54 23.99(1.91%) 534 - 872 0.25L-0.8Br 423 19.27

19.63 19.61(−5.19%)872 - 1136 −Br

15.00a

[NiBr2(3-clan)1.5] 392 - 395 3.11 3.08(−0.96%) 360 - 361 −0.1L 387 96.73

49.79 47.73(−4.86%)361 - 482 −1.4L 431 0.71

27.30 27.73(1.58%) 806 - 916 −1.4Br

21.82a

[CuBr2(3-clan)2] 446 - 450 31.99 32.29(0.94%) 376 - 415 −1.2L 393 57.22

10.66 11.18(−4.88%)415 - 552 −0.4 L

54.02 53.67(−0.65%)552 - 1005 −0.4 L-2 Br−0.75Cu

2.69a

[ZnBr2(3-clan)2] 387 - 390 39.84 40.12(0.70%) 450 - 485 −1.5L 537 74.45

9.30 9.34(0.43%) 485 - 658 −0.35L

44.43 45.19(1.71%) 658 - 712 −0.15L-2Br-0.6Zn

5.35a

aResidue at 1243 K. b(standard deviation errors).

Table 4. Band maxima and calculated ligand field parameters of the complexes.

Complex Band maxima(×103 cm−1) Interligand + charge transfer

d-d

1a Dq(cm−1)

[FeBr2(3-clan)1.5] 12.5 1250 25.27

[CuBr2(3-clan)2] 15.9 24.39

1b 2c 4d 3e Dq(cm−1) B(cm−1)Dq/B



(B/Bo)

[NiBr2(3-clan)1.5] 8.34 12.48 14.53 24.25 834 458 1.822 0.444 36.82

Key: aν1 = 5Eg5T2g; bν1 = 3T2g3A2g; cν2 = 3T1g(F)3A2g; dν4 = 1Eg3A2g; eν3 = 3T1g(P)3A2g;



= B/B0; B0 = 1030 cm−1 [37].

obtained for the dissolution enthalpies: (1Ho) for the

dissolution of MBr2 (solution a); (2Ho) for the dissolu-

tion of the ligand in the former solution, with respect to

the stoichiometry of the ligand in the later solution, re-

specting the stoichiometry of the complex (solution b);

and (3Ho) for the dissolution of the complexes (solution

c). This table presents the uncertainty intervals as twice

the standard deviation of the means of (3 - 6) replicate

measurements. Using thermochemical cycles [38] and

the calculated values for the enthalpies of reaction (5)

(rHo), the thermochemical parameters for the complexes

were estimated. Table 6 presents the values obtained for

these enthalpies.

4. Discussions

The standard enthalpy of decomposition is defined by the

equation:



 



2s l

MBr3-clanMBrn 3-clan;

  (6)

where .



oogo

Drl

n3-claHHHn

he standard lattice enthalpy is defined by

Open Access OJPC

P. O. DUNSTAN, A. M. KHAN 167

Table 5. Enthalpies of dissolution at 298.15 K.

Complex Calorimetric Solvent Number of i iH

experiments a kJ·mol−1

FeBr2(s) 1.2 M aq. HCl 5 1 −70.25  0.71

3-clan(l) 1.5:1 FeBr2-1.2M aq. HCl 5 2

−33.07  0.92

[FeBr2(3-clan)1.5](s) 1.2 M aq. HCl 4 3

10.50  0.44

NiBr2(s) 1.2 M aq. HCl 5 1

48.05  0.35

3-clan(l) 1.5:1 NiBr2-1.2 M aq. HCl 4 2

−35.83  0.86

[NiBr2(3-clan)1.5](s) 1.2 M aq. HCl 4 3

−14.94  0.36

CuBr2(s) 1.2 M aq. HCl 3 1

−17.98  0.13

3-clan(l) 2:1 CuBr2-1.2 M aq. HCl 3 2

−34.11  0.40

[CuBr2(3-Clan)2](s) 1.2 M aq. HCl 5 3

17.87  0.48

ZnBr2(s) 1.2 M aq. HCl 6 1

−39.13  0.60

3-clan(l) 2:1 ZnBr2-1.2 M aq. HCl 4 2

−48.04  0.88

[ZnBr2(3-clan)2[](s) 1.2 M aq. HCl 5 3

9.36  0.29

aExperimental data available after applying for.

Table 6. Summary of the thermochemical results (kJ·mol−1) for the complexes.

Complex rHo fHo s,1gHo MHo DHo rHo(g)



M-N

FeBr2(s) −249.8 [40] 204 [40]

NiBr2(s) −212.1 [40] 170 [40]

CuBr2(s) −141.8 [40] 182.4 [40]

ZnBr2(s) −328.65 [40] 159.7 [40]

3-clan(l) −11.8 [40] 61.9 [41]

[FeBr2(3-clan)1.5](s) −113.82  1.24 −381.3  3.1233  11 [39] −411  4206.7  3.2 −178  12 119  8

[NiBr2(3-clan)1.5](s) −68.94  1.00 −298.7  2.4199  11 [39] −332  3161.8  3.2 −133  11 89  7

[CuBr2(3-clan)2](s) −69.96  0.65 −235.4  4.5212  11 [39] −376  4193.8  4.1 −165  12 83  6

[ZnBr2(3-clan)2](s) −96.53  1.10 448.8  4.6 189  11 [39] −380  5220.3  4.1 −191  12 96  6



2g gn

MBrn 3-clanMBr3-clan;



 



(7)

where



oogo

MDs

MBrHHH 2

The standard enthalpy of reaction in the gaseous phase

is defined by the equation:







2g gn

MBrn 3-clanMBr3-clan;gH



 



(8)

where



ogo go

rs l

2s l

ogo

rs s

gMBrn3-cl

complex

HH H

 

 

As the complexes decomposed on heating, the enthal-

pies of sublimation of the adducts were estimated [39].

The standard enthalpies of the metal(II)-nitrogen bonds

are obtained from reaction (8) [40]:











M-N . Table 6 presents the values

obtained for all of the enthalpies. The formation enthal-

pies of the complexes in the gaseous phase according to

reaction (9):

gnDH

 







2 o

gg gng

M2Brn 3-clanMBr3-clan;I

 







(9)

are equal to:















fI ff

complex M

2Brn3clan

HH H

 

 

 

 .

Table 7 presents the values obtained for these en-

thalpy values. The acidity order was obtained based on

the rH



or D values for the complexes. Complexes of

Open Access OJPC

P. O. DUNSTAN, A. M. KHAN

168

Table 7. Auxiliary data and enthalpy changes of the ionic

complex formation process in the gaseous phase (kJ·mol−1).

Compound fH



rH



(g) fIH



Br(g)- −219.07 [42]

Fe(g)2+ 2751.6  2.3 [42]

Ni(g)2+ 2930.5  1.5 [42]

Cu(g)2+ 3054.5  2.1 [42]

Zn(g)2+ 2781.0  0.4 [42]

[FeBr2(3-clan)1.5](g) −149  12 -178  12 −2742  12

[NiBr2(3-clan)1.5](g) −100  11 -133  11 −2668  11

[CuBr2(3-clan)2](g) −24  12 -165  12 −2741  13

[ZnBr2(3-clan)2](g) −260  12 -191  12 −2922  12

the same stoichiometry were compared. The acidity order

is: FeBr2 > NiBr2 and ZnBr2 > CuBr2. The basicity order

was obtained based on the rH



values of the complexes

of 3-clan and 4-clan [42] of the same stoichiometry. The

basicity order is: 3-clan > 4-clan (for CuBr2) and 3-clan >

4-clan (for ZnBr2). Comparing the rH



values for com-

plexes of aniline (an) [43] of the same stoichiometry, the

basicity order is: an > 3-clan (for CuBr2) and an > 3-clan

(for ZnBr2). As a whole, the basicity order is: an > 3-clan

> 4-clan (for CuBr2 and ZnBr2). Using t heD values

the order is: an > 4-clan > 3-clan (for CuBr2 and ZnBr2).

The expected order would be: an > 3-clan > 4-clan be-

cause the inductive effect of the electron withdrawing

chloro atom, which causes the diminution of the elec-

tronic density in the aromatic ring and of the electronic

density available for the nitrogen atom linked to the ring.

The chlorine atom withdraws more electronic density in

the para-position than in the meta-position. This means

that the D parameter is better than the rH



parameter

for determining the basicity order. This could be due to

the contribution of another kind of interaction in rH



like hydrogen bonding (Cl-----H) in the 3-clan addut.

5. Conclusion

Solid complexes were obtained through the interaction of

3-chloroaniline with bromides of the first row of divalent

transition metals. These complexes were decomposed upon

heating. The determination of the enthalpies of solution

of the adducts, salts and ligand leads to the estimation of

the energies of the metal ion-nitrogen coordinated bonds.

The values were between 82 and 119 kJ·mol−1. As a

whole, the basic strength of 3-chloroaniline with respect

to aniline and 4-chloroaniline is an >3-clan > 4-clan, as it

would be expected by the inductive effect of the electron

withdrawing chlorine atom, which is stronger in the para-

position than that in the meta-position.

6. Acknowledgements

Majeed Khan thanks TWAS/CNPq organizations for a

fellowship which made it possible for him to undertake

the above research at the University of Campinas.

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