UNIVERSITY OF SANTO TOMAS

FACULTY OF PHARMACY
PHYSICAL CHEMISTRY

Determining the Relationship between Equilibrium Constants and Temperature

using the van’t Hoff Equation
Atienza, Jonas James R., Butalid, Marie Diane A., Calpo, Rizelle Anne A.,
Segui, Dana Isabelle A., Yow, Mark Nicholas L.
GROUP V
2B - BC

ABSTRACT

The change in the equilibrium constant (K) of a reaction with relation to change in
temperature (T), given the standard enthalpy change (∆Ho) for the process is explained
quantitatively by van’t Hoff equation. The experiment aims to determine the relationship between
equilibrium constant and temperature in a reaction, also explain its relationship with standard
enthalpy of the reaction. It was performed in a constant temperature (298.15 K) and atmospheric
pressure (750.8 mmHg) of the area. In a hard glass tube containing naphthalene with toluene
was used as a sample, placing a copper wire as a stirrer for the solution. The sample was
submerged in a water bath with constant stirring until dissolution of naphthalene with toluene
was achieved for the temperature to be taken note. The procedure was repeated various times
until a three (3) more one (1) mL portion of toluene was added. Data gathered was used to
compute for the slope (via linear regression), and heat of solution using van’t Hoff equation. The
slope, and heat of solution in the experiment was -2669.40, and 22193.39, respectively.

INTRODUCTION

Le Chatelier’s principle states This equation was derived from,

that any system at equilibrium on a long
period of time is exposed to change ΔrGo
∂[ T ] −𝚫rHo
in concentration, temperature, ( )P = −
∂T 𝐓2
volume, or pressure of the system
changes to a new equilibrium and this
change partly counteracts the applied in which the temperature dependence of
change (Gall, 2002). K was shown.

Van’t Hoff equation is used to Then this equation can be further derived
determine the equilibrium of a chemical to:
reaction at a constant temperature. The ∂[𝑙𝑛𝐾] −𝚫rHo
equilibrium constant, K values can be ( )P =−
∂T 𝐓2
changed with the change of temperature.
The following is derived from Gibbs-
Helmholtz equation (Bevensee, 2013).
 UNIVERSITY OF SANTO TOMAS
FACULTY OF PHARMACY
PHYSICAL CHEMISTRY
If temperature is changed that
ΔrH is considered constant, it can be
o
translate by a K value at a temperature
into another by integrating the above
expression (Atkins, 2006).
𝐾2 −𝛥𝑟𝐻 𝑜 1 1
𝑙𝑛 =− ( − )
𝐾1 𝑅 𝑇2 𝑇1
Where 𝑇1 and 𝑇2 are denoted as the
absolute temperatures at condition 1 and
2 respectively;
𝐾1 and 𝐾2 are denoted as the equilibrium
constants of 𝑇1 and 𝑇2 respectively;
−𝛥𝑟𝐻 𝑜 is denoted as the standard molar
enthalpy of the reaction and R is the gas
constant.
The purpose of this experiment is
to be able to measure the equilibrium
constants at different temperatures; be
able to generate a temperature-
equilibrium constant diagram; determine
the relationship of temperature and
equilibrium constants; and be able to
approximate the standard molar enthalpy
of the reaction using the temperature-
equilibrium constant values.
METHODOLOGY
The materials that were used in
this experiment were, a 250 mL of
beaker, hard glass test tube, 10 mL
pipette, thermometer, cork with hole,
copper wire, hot plate, aspirator,
naphthalene and toluene.
Starting the experiment by
weighing 10.00 g of naphthalene in a
hard glass test tube, then using a pipette
5.00 mL of toluene was poured inside
the test tube containing naphthalene. The
test tube was then covered with a cork,
then a thermometer and a copper wire
stirrer were inserted in the hole of the
cork. The test tube was then hot bathed
using a 250.0 mL of beaker half-filled of
water. The test tube was then constantly
stirred using the copper wire stirrer.
Once the naphthalene was all dissolved
into the solution the temperature was
noted. Afterwards, the test tube was then
placed under running water in order to
solidify again. After it solidifies, about
1.00 mL of toluene was added inside the
test tube, it was then placed in the hot
bath to liquify. This step was repeated
until the volume of the toluene inside the
test tube was 8.00 mL.
The concentrations and
equilibrium constants of naphthalene in
toluene was then computed and was
graphed against the solubility
temperature. The slope was then
determined using linear regression and
the heat of solutions was determined
using the van’t Hoff equation.
 UNIVERSITY OF SANTO TOMAS
FACULTY OF PHARMACY
PHYSICAL CHEMISTRY

RESULTS AND DISCUSSION

Van’t Hoff equation is an Differentiating with respect to

equilibrium of a chemical reaction temperature at constant pressure
constant at a given temperature.

Table 1. Environmental Conditions

Temperature
24°C Comparing the above two-equation,
Atmospheric
Pressure 750.8 mmHg

The greater the value of the

The quantitative relation
standard enthalpy of a reaction, the faster
connecting chemical equilibrium and
the equilibrium point is reached by the
temperature can be expressed through
chemical reaction.
the Gibbs-Helmholtz equation below.

The van’t Hoff equation

Derivation of the Gibbs – Helmholtz
equation

Zero superscripts are indicating stranded In the experiment, van’t Hoff

values. solubility method was used in
determining the integral heat of solution
of naphthalene in toluene. Naphthalene
and toluene, both non-polar compounds,
were used to determine the heat of
solution. The physical properties of both
compounds are shown in Table 2.
The van’t Hoff isotherm
 UNIVERSITY OF SANTO TOMAS
FACULTY OF PHARMACY
PHYSICAL CHEMISTRY

Table 2. Physical properties of Naphthalene and Toluene (Bennett, n.d.)

Compound Naphthalene Toluene

Structure

Molecular Formula C10H8 C7H8

Molecular Weight 128.17 g/mol 92.14 g/mol
Density 1.14g/mL 0.8623 g/mL
Melting point 353.45K 178.15K
Boiling point 491.15K 384.15K
The behavior of the solubility of whereas induced-dipole-induced-dipole
the two compounds and the heat of interaction is exhibited in toluene. When
solution is dependent on the strength of these two compounds are mixed, their
their intermolecular interactions. The intermolecular of different strengths,
intermolecular attraction that exists in make their behavior almost that of an
naphthalene is the Van der Waals force, ideal mixture (Atkins, 2014).

Table 3. Four Flasks with Varying Concentration and Dissolution Temperature

Set Up Mass of Volume Concentration Dissolution Temperature (K)

Naphthalene of Trial 1 Trial 2 Trial 3
Toluene
1 10.0 g 5 mL 16.6 M 353.15 K 355.15 K 354.15 K
2 10.0 g 6 mL 13.0 M 343.15 K 343.15K 343.15 K
3 10.0 g 7 mL 11.1 M 338.15 K 339.15 K 338.15 K
4 10.0 g 8 mL 9.75 M 333.15 K 333.15 K 333.15 K

To determine the heat of solution of against ln, by equating the slope to the
naphthalene in toluene, the graph of van’t Hoff equation.
1/T obtained from Table 3 was plotted

Table 4. Values of X and Y for the linear graph

 UNIVERSITY OF SANTO TOMAS
FACULTY OF PHARMACY
PHYSICAL CHEMISTRY

1/Temperature (1/K) ln X of naphthalene

0.002824 2.75
0.0029142 2.56
0.002953 2.41
0.003002 2.28

Concentration vs Dissolution Temperature

lnX of Naphthalene

y = -0.156x + 2.89
R² = 0.9930

1 2 3 4
1/Temperature (1/K)

Figure 1. Linear graph of Graph of Concentration vs Dissolution Temperature of Four

Different Flasks varying in Concentration
∆𝐻 𝑜 1
𝑙𝑛 𝐾 = − ( )
The equation of the line, 𝑅 𝑇
y = -0.156x+2.89
In relation to the slope equation:
from y = a + bX; where,
X is the variable 𝑦 =𝑚𝑥+𝑏
Y is the dependent variable
b is the slope of the line where y is denoted as the natural
a is the intercept logarithm of K (ln K), m as the negative
in change in enthalpy for the reaction
was used to determine the heat of ∆𝐻 𝑜
over gas constant (- [ ]) and x as the
solution of naphthalene. The calculations 𝑅
1
are as follows: reciprocal of temperature (𝑇).

In relation to the van’t Hoff

Equation, K is denoted as the
 UNIVERSITY OF SANTO TOMAS
FACULTY OF PHARMACY
PHYSICAL CHEMISTRY

equilibrium constant, ∆𝐻 𝑜 as the change

in enthalpy for the reaction, R as the gas
constant, and T as temperature.

Table 5. Values of X and Y for the linear graph of Dissolution Temperature vs

Concentration

Equilibrium constant, K (y)

SET UP Temperature, (x; 1/T)
1 354.15 = 0.002824 ln 13.6 = 2.747
2 343.15 = 0.0029142 ln 13.0 = 2.565
3 338.65 = 0.002953 ln 11.1 = 2.407
4 333.15 = 0.003002 ln 9.75 = 2.277

r = (-0.9903)2 = 0.98109 m (slope) = -2669.40

Figure 2. Linear Graph of Relationship between Concentration and Dissolution

Temperature

The reaction was known to be
endothermic because the obtained standard
molar enthalpy is positive. Van’t Hoff
equation drowns the relation between
equilibrium constant and endothermic and
exothermic chemical reactions. For an
endothermic reaction, ΔH0, zero (0), and
the right-hand side of the equation
positive. This leads to the fact that natural
logarithm of K increases with increasing
temperature and decreases with reciprocal
of temperatures. (Angulo-Brown & Arias-
Hernandez, 1996).
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FACULTY OF PHARMACY
PHYSICAL CHEMISTRY

Van’t Hoff equations give a quantitative and temperature of dissolution. It has

expression of the Le-Chatelier principle.
Whenever a stress is placed on
any reaction system in a state of
equilibrium, the system will always shift
in a direction to reduce the applied
stress.
A direct relationship is evident
between concentration of naphthalene
direct relationship with one another.
Furthermore, increased temperature
favors shift towards the product side as
mentioned by Le Chatelier (Bennett,
n.d.).
Comparing the data obtained
from a similar study, the concentration
for every set up was computed in terms
of the ratio of mole of naphthalene and
the total mole of mixture.

Table 6. Values of X and Y for the linear graph of a similar study (Carreon et al., n.d.)

1/Temperature (1/K) ln X of naphthalene

0.002914177 -0.469843642
0.002926972 -0.469843642
0.002939879 -0.542144307
0.002966039 -0.609541597
0.002973094 -0.672756491

Both data showed direct relationship
between the two variables. However, the
data retrieved from other study showed
negative values for lnX of naphthalene. The
temperature increased in a chemical
reaction, the system at equilibrium point
moves in a direction in which heat absorbed,
which is favored by an endothermic
reaction.
CONCLUSION
Based from the data gathered, it
showed that as the temperature of the
dissolution of naphthalene increases,
equilibrium constant decreases thus, the
relationship between temperature and
equilibrium constant is inversely
proportional. It also showed that the greater
the value of the standard enthalpy of a
reaction, the faster the equilibrium point is
reached by the chemical reaction. Increased
temperature favors shift towards the product
side. From the results obtained and with the
use of linear regression, it was also
concluded that temperature-equilibrium
constant has an inverse linear relationship
given that the computed slope was -2669.40
and the heat of solution at 22193.39 J/mol-
K.

REFERENCES
 UNIVERSITY OF SANTO TOMAS
FACULTY OF PHARMACY
PHYSICAL CHEMISTRY

Angulo-Brown, F., & Arias Hernández,

L.A. (1996). van’t Hoff’s Equation for
Endoreversible Chemical Reactions. The
Journal of Physical Chemistry, 100(21),
9193 9195. doi:10.1021/jp953017q

Atkins, P., de Paula, J. (2014). Atkins’

Physical Chemistry 10th Edition. Oxford
University Press.

Atkins, Peter; De Paula, Julio (10 March

2006). Physical Chemistry (8th ed.). W.
H. Freeman and Company. p. 212. ISBN
978-0-7167-8759-4.

Bennett, P. (n.d.) Chemical

Thermodynamics. Retrieved from
http://www.geo.utexas.edu/courses/376
m/lecturenotes/thermo.pdf

Bevensee, M; Boron, W. (2013). Seldin

and Giebisch's The Kidney (Fifth
Edition). Academic Press. ISBN 978-0-
12-381462-3.

Gall, J. (2002). The Systems Bible (3rd

ed.). General Systemantics Press. The
System
always kicks back

Lone IH. (09 June 2017). The

Alternative Formulation of Van't Hoff
Equation. Phys Chem Ind J.
2017;12(2):110.
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FACULTY OF PHARMACY
PHYSICAL CHEMISTRY