Christian Villaran

TA: Chase Zachary

Determination of an Equilibrium Constant

Abstract:
This lab is aimed at finding how the equilibrium constant of a reaction will change with change
in temperature. We can do this by finding the percent transmittance at different temperatures. From this
we can solve for concentrations of both the xylenol orange and the aluminum. These concentrations are
precisely what we need to find K. Once we find K we can use vant Hoff’s equation to look at some of the
thermodynamic properties (enthalpy and entropy) by making a graph of (1/T) versus ln K. In using this
equation we are making the assumption that change in enthalpy is constant at different temperatures,
and by looking at the graph we will be able to decide if this is a fair assumption. The values I got for
change in enthalpy and change in entropy were 99658 J/mol and 199 J/K∙mol, respectively. Because the
ln K values form a line when graphed, the assumption that change in enthalpy is constant at different
temperatures can be said to be a fair one.

Background:
The purpose of this lab is to find the K value of a reaction and to see its dependence on change
in temperature. By using vant Hoff’s equation and plotting it as a graph of (1/T) versus ln K we can also
find the change in enthalpy and change in entropy of the reaction. In this way we can calculate
thermodynamic properties of the equilibrium reaction, and decide if some of the thermodynamic
assumptions we usually make are approximately true.

Key Equations:

H4Q(aq) + Al+++ QAl- + 4H+

A = -log10(transmittance)

[Al at equil] = [Al initial] – [AlQ at equil]

[H4Q at equil] = [H4Q initial] – [AlQ at equil]

A = ЄlC = Єl[AlQ at equil]

K= [AlQ at equil][H+]4__
[Al at equil] [H4Q at equil]

ln K = -ΔH⁰ (1/T) + ΔS⁰

R R

Procedure:
See Pg. 34 of A General Chemistry Lab Manual: The Rediscovery Book
(No changes to the written procedure)

Observations:
When the mixtures were being heated in the warm water bath it was apparent that as the temperature
went up, the color became darker. Originally the color was a light almost transparent orange. At 95
degrees Celsius the color was almost a red orange and had very little transparency.
The color in the ice bath was very similar to the color at the very end of the heating process. It continued
to be a darker orange/red orange color.

Data and Calculations:

(See attached sheet for calculations and graphs)

Discussion:
This lab had two main aims. The first was to find K, as well as its dependence on temperature.
The second was to use these values of K in vant Hoff’s equation and use the idea of slope and y-
intercepts to find thermodynamic properties enthalpy and entropy.
If you look at the data and calculations section there are a few observations that can be noted.
The first is that with an increase in temperature the percent transmittance goes down. Because the
percent transmittance is going down the absorbance is going up. The absorbance is what affects the
color that we see. This is because absorbance is related to the intensity of the light waves. The higher the
absorbance the higher the intensity of the waves will be, and the higher concentration of the molecule
(AlQ) will be. The steady decrease in concentration of the AlQ as the temperature decreases can also be
seen in the data section on the next page. Therefore, as the temperature goes up we see a brighter color
of red/orange due to the higher intensity of the waves and higher concentration of AlQ in the tube.
The tube in the ice bath seems to be the exception to this rule. Using the fact that higher
temperatures mean brighter colors due to higher intensity we would assume that the ice bath would be
the lightest color of all the other temperatures. From observations, however, we see that the tube in the
ice bath remained a bright orange, and even had a K value that was closest to the highest temperature K
value. This can be accounted for by the drastic change in temperature. The system was not allowed to
reach equilibrium in a smooth continuous manner but instead was jolted from one extreme temperature
to another. This caused the system to “freeze” and stay at the state it was at high temperatures. For this
reason the color and K value are similar to those at high temperatures.
Other important pieces of data are the K values for the different temperatures. From the chart in
the data and calculation section we can see that as the temperature goes up the K value also goes up.
Since K value is calculated by dividing the concentrations of the products by the concentrations of the
reactants, an increase in the K value means an increase in the products (the numerator). From this we
can say that with an increase in temperature the system moves to the right towards the products. This is
a characteristic of endothermic reactions.
When we graphed the vant Hoff’s equation as a function we found that it was indeed a linear
function. With the general linear formula of y = mx + b we found that ln K could be y, 1/T could be x with
the slope (m) equal to negative change in enthalpy over R, and b could equal change of entropy over R.
From the best fit line we can find the estimated slope and find change in enthalpy. I found my value of
change of enthalpy to be 99658 J/mol. The positive change in enthalpy supports the conclusion that this
reaction is endothermic.
Using the y-intercept estimated by the best fit line and the fact that b equals change of entropy
over R, change in entropy could be calculated. The value I got was 199 J/K mol. This positive value for
change in entropy is expected. The color is expected to spread through the tube as the reaction takes
place because there are more microstates with the color distributed than with the color in one spot. The
theoretical change in entropy should therefore by positive.
Usually when doing thermodynamic problems it is assumed that change in enthalpy and change
in entropy are constant at different temperatures. Since the ln K values at different temperatures did in
fact form a line when graphed, the vant Hoff’s equation can be concluded to hold true for most
temperatures. This also implies that holding change in enthalpy constant in these problems is a fair
assumption to make.