International Journal of Mechanical Engineering and Technology (IJMET)

Volume 9, Issue 13, December 2018,

201 pp. 14–19, Article ID: IJMET_09_13_002
Available online at http://www.iaeme.com/ijmet/issues.asp?JType=IJMET&VType=9&IType=13
ISSN Print: 0976-6340 and ISSN Online: 0976-6359

© IAEME Publication Scopus Indexed

EFFECT OF SOLVENT ON THE

CONDUCTANCE OF TETRAMETHYL
TETRAMETHYL
AMMONIUM BROMIDE IN AQUEOUS N, N-
N
DIMETHYL FORMAMIDE
V. Radhika, K. Srivani
Department of Chemistry, S R Engineering College, Urban Warangal 506371, India

N. Srinivas
Department of Chemistry, Kakatiya University, Urban Warangal 506009, India

M. Rajya Laxmi
Department of Business Management, S R Engineering
Engineering College,
Urban Warangal 506371, India

ABSTRACT
The conductance of Tetramethyl ammonium bromide has been studied in water -N,
N-dimethyl
dimethyl formamide mixtures of different compositions in the temperature range
303-318K.
318K. The molar conductance data collected
collected at different concentrations of the
electrolyte is analyzed using Shedlovsky and Krauss - Bray models. The limiting molar
conductance is found to be dependent on the temperature and dielectric constant of
the medium. Increase in temperature and decrease
decrease in dielectric constant of the aquo-
aquo
organic mixture increase the limiting molar conductance values. From these effects,
the activation energy of the conducting process and distance of separation between
the ions are calculated. From the effect of temperature
temperature on the ion pair association
constant KA, the enthalpy change accompanied by the ion pair formation is
calculated. The solvation number computed in each solvent suggests that, the solvent
solute interactions are dependent on the dielectric constant of the medium.
Keywords: Ion - Pair Association Constant, Ion-Pair
Ion Pair Dissociation Constant, Solvation
Number, Tetra Methyl Ammonium Bromide.

Cite this Article: V. Radhika, K. Srivani, N. Srinivas and M. Rajya Laxmi, Effect of
Solvent On The Conductance of Tetramethyl Ammonium Bromide In Aqueous N, N- N
Dimethyl Formamide, International
International Journal of Mechanical Engineering and
Technology, 9(13),), 2018, pp. 14–19.
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 V. Radhika, K. Srivani, N. Srinivas and M. Rajya Laxmi

1. INTRODUCTION
Conductance studies in single and mixed solvent systems have continued to be of great
interest to chemists. The literature is replete with conductance data of many electrolytes in
aqueous, organic and in binary organic solvent systems. The conductance behavior of many
ions in mixed solvent systems is reported to be influenced by a number of factors including
solvent solute interactions, solvent - solvent interactions, densities and viscosities of the
mixed solvent systems and the extent of solvation of the ionic species.
Literature survey Manikyamba et al1-15 indicates that, the conductance data and viscosity
data of different electrolytes is useful in analyzing the ion solvent interactions and solvation
behavior of the ions.
The present work deals with the conductance behavior of Tetramethyl ammonium
bromide in aqueous N, N-dimethyl formamide at different temperatures between 303 and 318
K. In the present communication the results of these studies are presented.

2. EXPERIMENTAL SECTION
Deionzied water was distilled and used. N, N-dimethyl formamide (DMF) (Sd-fine) was used
as such. Tetramethyl ammonium bromide (Spectrochem) sample is also used without further
purification. A conductivity bridge (ELICO. Model - 180) equipped with a glass conductivity
cell of cell constant 0.9845cm-1 was used to measure the conductance of the solution, The
cell is calibrated using standard (0.1M) KCl solution. The precision of the conductivity bridge
is ± 10µS . A stock solution of 0.05M Tetra methyl ammonium bromide was prepared in water
/ aqueous organic solvent mixtures of different compositions (v/v) in the range 0 to 80%
organic component. The solute was found to be insoluble above this composition. i.e. 90%
and 100% organic solvent . The solution was diluted to different concentrations using
different volumes of solvent/ solvent mixture and the conductance values were measured in
the temperature range 303-318 K. The solvent / Solvent in the mixture used in these studies
have conductance values in the range 20-40 µS. The conductance of the solvent was
subtracted to get the conductance of the solute at each concentration. The molar conductance
values calculated from the observed conductance are analyzed using Kraus-Bray equation16
and Shedlvosky equation 17 (eqn2)
1 ∧C 1
= +
∧ K C ∧ 20 ∧ 0
- (1)
2
1 Sf K A C ∧ 1
±
= +
S∧ ∧ 20 ∧0 (2)
Λ is molar conductance at concentration C, Λ 0 is the limiting molar conductance. K A is
the association constant of the ion pair, KC is the dissociation constant, f ± is the mean ionic
activity coefficient, S is a factor given by
2
Z  Z 
2

S =  + 1+   
 2  2 
 (3)
 α ∧ 0 +β  1/ 2
Z= 3/ 2  (C ∧ )
 ∧ 0 
Where (4)
 1 1/ 2
β = 82.50  (∈T)
 η (5)

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 Effect of Solvent On The Conductance of Tetramethyl Ammonium Bromide In Aqueous N, N-
Dimethyl Formamide

is the dielectric constant η is the viscosity of the medium. ∝= 8.204 x10 5 (∈ T ) S is

3/ 2
∈
calculated using Λ 0 obtain from the On sagar model using the plot of Λ against C. The
least square analysis of the using the above two equations (1,2) is satisfactory with linear
correlation coefficients in the range 0.93-0.96.

3. RESULTS AND DISCUSSION

The molar conductance ( Λ ) was determined from the solvent corrected specific conductance
for tetramethyl ammonium bromide in water, DMF, in various compositions (v/v) of water -
DMF mixtures at 303, 308, 313 and 318 K. The values were analyzed using Debye- Huckel -
Onsagar, Kraus - Bray and Shedlovsky models of conductivity to evaluate molar conductance
at infinite dilution Λ 0 . The values thus obtained are shown in Table-1.

Table 1 Limiting molar conductance values in S cm2mol-1 of tetramethyl ammonium bromide in water
-DMF mixtures.
0% DMF 20% DMF 40% DMF 60% DMF 80% DMF
T(K)
(1) (2) (1) (2) (1) (2) (1) (2) (1) (2)
303 123.3 123.4 85.2 85.1 83.1 83.2 35.7 35.7 31.3 31.3
308 154.5 154.5 104.8 104.8 100.8 100.8 46.8 47.4 36.5 36.4
313 174.3 174.2 113.9 114.0 133.9 134.0 49.8 50.0 39.9 40.0
318 189.2 189.1 125.0 124.9 134.4 134.3 52.6 52.6 46.7 46.6
1- Shedlvosky model 2- Kraus Bray model
Expected values increase with increase in temperature in all the cases due to increase in
thermal energy and mobility of the ions. Limiting molar conductance values are observed to
be dependent on composition of the solvent also. At each temperature these values are
maximum in pure water. With the addition of DMF to water they gradually decrease. The
composition of DMF could not be extended beyond 80% as TMAB was not soluble.
The decrease Λ 0 is due to increase in the proportion of DMF may be due to decrease in the
dielectric constant of the medium. On adding co-solvent to water, solvent - solvent interaction
increases. Since conductivity increases with increase in temperature, it is supposed that this
variation has to follow Arrhenius relation18 like rate process, Λ 0 = Ae − Ea / RT , Ea is the energy
of activation of rate process, R is gas constant and T is the temperature on absolute scale.
1
From the slope of the linear plot of versus , Ea is evaluated. The Ea values are tabulated in
T
Table-2. There values appear to be highly dependent on solvent composition. In DMF-water
mixture Ea value is maximum at 100% water.

Table: 2 Computed thermodynamic parameters for tetramethyl ammonium bromide under varying
compositions (v/v) water-DMF mixtures.
T(K) 0% DMF 20% DMF 40% DMF 60% DMF 80%DMF
Ea (K.J.mol-1) 19.2 16.81 23.2 17.16 17.06

4. ASSOCIATION AND DISSOCIATION CONSTANT:

From the slopes of the linear least square analysis using Kraus-Bray and Shedlovsky models,
the association constant (KA) and the dissociation constant (KC) of the ion pair have been
evaluated and presented in Table 3. KA values decrease with the increase in temperature in

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 V. Radhika, K. Srivani, N. Srinivas and M. Rajya Laxmi

0%, 20%, 40% (v/v) DMF- water mixture, indicating the exothermic behavior of the system.
At all other compositions KA values increase with increase in temperature, indicating the
endothermic behaviors of the system. i.e. ion pair formation is accompanied by absorption of
heat.

Table 3 KA and KC values of tetramethyl ammonium bromide in water - DMF mixtures.

T(K) 0% DMF 20% DMF 40% DMF 60% DMF 80% DMF
KA KC KA KC KA KC KA KC KA KA
303 4.16 0.24 3.54 0.28 28.40 0.03 12.61 0.08 10.41 0.10
308 5.61 0.18 5.10 0.20 29.34 0.034 11.92 0.083 7.17 0.14
313 5.77 0.17 5.20 0.19 30.23 0.032 8.12 0.12 6.80 0.14
318 7.00 0.14 5.50 0.18 31.25 0.03 7.57 0.13 5.21 0.19
The data presented in Table-3 indicates that KA values vary due to change in the
composition of the solvent mixture also. This shows that ion pair formation is influenced by
the dielectric constant of the medium. Maximum KA value is observed in 40% (v/v) DMF-
water mixture.

5. SLVATION NUMBER
The solvation number (Sn) which is the number of solvent molecules in the solvent around
the species is calculated from the effect of dielectric constant ∈ on Λ 0 based on the equation
Z A Z Be 2
log∧ 0 = log∧10 −
∈ d AB k BT (6)
ZAe, ZBe are the ionic charges, kB is Boltzmann constant, T is the temperature and dAB is
the distance between the centers of the two ions Λ 0 is liming molar conductance in solvent of
infinite dielectric constant. The plot of log Λ 0 against 1/ ∈ is linear and from the slope of this
plot, is computed. Sn is computed using the relation,
d AB − ri
Sn =
rsolvent
- (7)
Where ri is the Stokes radius of the ion calculated using the equation19
0.820 z
ri = + 0.0103 ∈+ ry
∧ 0 η0 - (8)
Where ry=0.85A0 for dipolar unassociated solvents and 1.13A0 for protic and associated
solvents.

Table 4 Solvation number for tetramethyl ammonium bromide in various compositions of water -
DMF mixtures at 303K
0% DMF 20% DMF 40% DMF 60% DMF 80% DMF
0.65 1.00 0.71 0.65 0.38
The solvation number data of the ion thus determined at 303K in all the binary solvent
systems studied is shown in Table-4. These values are nearly constant except in 80% (v/v)
DMF water mixture. Suggesting that the ion- solvent interactions are nearly independent of
the composition of the aquo organic solvent mixture. In 80% (v/v) DMF - water-mixture the
solvation number is slightly less. This is attributed to a decrease in the interaction between the
ion pair and the solvent.

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 Effect of Solvent On The Conductance of Tetramethyl Ammonium Bromide In Aqueous N, N-
Dimethyl Formamide

6. CONCLUSION
The conclusion from these experimental observations that ion-ion interactions are strong in
higher percentage of DMF while ion-solvent interactions are weaker in DMF compared to
other solvent mixtures for all three electrolytes.
Ethical clearance - Not required
Source of funding - Self
Conflict of Interest- NIL

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