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
Received August 13, 2013; revised September 10, 2013; accepted September 18, 2013
Copyright © 2013 Pedro Oliver Dunstan, Abdul Majeed Khan. This is an open access article distributed under the Creative Com-
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)
A
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]:

o
1 2s
MBrselected solventsolution a;
H
 (1)



o
2
1
n3-clansolution asolution b;
H
  (2)



2ns
o
3
MBr3-clanselected solvent
solution c;H




(3)
o
4
solution bsolution c;
H
 (4)
According to Hess’law for the reactions (1)-(4), the
standard enthalpy of reaction (rH

) of the following
reaction:
 




o
2r 2s lns
MBrn 3-clanMBr3-clan;
H
 


o
(5)
is equal to: ooo
r123
H
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:

 

o
2D
2s l
n
MBr3-clanMBrn 3-clan;
H
  (6)
where .

oogo
Drl
n3-claHHHn
T
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
D
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





o
2M 2g gn
s
MBrn 3-clanMBr3-clan;
H

 

(7)
where

oogo
MDs
MBrHHH 2
The standard enthalpy of reaction in the gaseous phase
is defined by the equation:







o
2r 2g gn
g
MBrn 3-clanMBr3-clan;gH   

(8)
where







ogo go
rs l 2s l
ogo
rs s
gMBrn3-cl
complex
HH H
HH
 
 
an
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]:





o
r
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
2f
gg gng
M2Brn 3-clanMBr3-clan;I
H
 



(9)
are equal to:










2
fI ff
gg
ff
gg
complex M
2Brn3clan
HH H
HH
 
 
 
 .
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
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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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