THERMODYNAMICS OF THE UREA-WATER SYSTEM

Online lab

Introduction
The Gibbs-Helmholtz equation (1) expressed at standard conditions offers an opportunity
for evaluating enthalpy (Δ H°), free energy (Δ G°), or entropy (Δ S°) changes, as desired.
ΔG° = ΔH° - T ΔS° (1)
This experiment describes a procedure to measure both Δ H° and Δ G° for mixing urea
with water, at a certain temperature, and then using equation (1) to calculate the corresponding
entropy change ΔS° for this mixing.
Part I. Enthalpy Measurements the Data is in the Table Part 1.
1. A student in lab will perform the lab and you will use this person's data to complete the
calculations and find all the necessary quantities to do the calculations. A certain student
we will call Zamdot will use a coffee cup calorimetry format in which two sytrofoam cups
are nested inside one another with a piece of foam set over the top and a thermometer
inserted into the foam as shown:

2. Zamdot carefully measures the mass of about 30 ml of H2O in a styrofoam cup, and records
the water temperature to the nearest 0.1 degree. Using the molar mass of urea (60.1 g/mol)
Zamdot calculates the grams he must add to the H2O to make a 1.00 M solution. Zamdot
checks his calculations carefully just as you would if you were in lab.
3. Before adding the urea to the H2O, the student takes one more temperature reading. Then
he mixes in the urea and records the temperature of the occasionally-stirred solution every
30 seconds for about 2 minutes. From this he finds the initial temperature and largest
temperature change to find ΔT
4. You will calculate ΔT experienced by the water; then use equation (3) below to calculate
the heat transferred during the dissolving process:
ΔT = Tfinal - Tinitial (2)
 QR = – [(mH2O) (CH2O) (Δ T) + (murea) (Curea) (Δ T)] (3)
where m represents the mass and C the heat capacity of each substance.

For H2O, the heat capacity is 4.184 J/g deg;. The presence of a minus sign indicates
direction of heat flow. Finally, calculate ΔH° (assuming standard state conditions apply)
from
Δ H° = QR (4)
moles of urea

and round off to kJ/mole. Is the reaction exothermic or endothermic? Does the sign on
your enthalpy agree with this?
5. Discard the urea solution, dry out the cup, and repeat the experiment two more times. Do the
described calculations for each trial, and finally calculate an average Δ H° ± average deviation.

Part II. Free Energy Measurements

1. The plan is to prepare a saturated solution of urea in water. Its equilibrium constant can
then be measured for the process urea + H2O  urea (aq). Then, the free energy change
is calculated from
ΔG° = - RT ln Keq (5)
2. Zamdot weighs a dry 10 ml graduated cylinder. Transfer 2 to 3 g of urea to the cylinder,
and record the combined weight.
3. Carefully and slowly with mixing he adds small increments of pure water with a clean
eyedropper until the urea just completely dissolves. He stirs the solution with his
thermometer waiting patiently for the temperature to return to near 20°C
4. He record the ml water level reached in the graduated cylinder, then obtains the total
weight of the solution. Zamdot keeps careful records of all the measurements. He also
writes down the temperature of the solution which is 22.0˚
5. The calculation for the equilibrium constant in this experiment has the form:
[𝑢𝑟𝑒𝑎]
𝐾𝑒𝑞 = (6)
𝑓𝐻2𝑂
 Since this saturated solution contains a high concentration of solute, the usual omission of
the solvent H2O from the form of Ke leads to an error of a factor of 100. In this saturated
solution the [H2O] is not the same as that of pure H2O, so to account for this change; you
must include this factor in equation (6). The factor ƒ represents the fraction of H2O in the
saturated solution relative to its pure state.

[𝐻2 𝑂]𝑖𝑛 𝑢𝑟𝑒𝑎 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

𝑓𝐻2𝑂 = [𝐻2 𝑂]𝑝𝑢𝑟𝑒
(7)

6. In pure liquid water, the [H2O] is 55.6 moles/L. Use your solubility data to calculate
[H2O] in your saturated solution. First figure out how many grams of H2O was added to
make the solution by carefully extracting its mass from the weighings made in steps 2 to
4.
7. Calculate the moles of H2O added, use the volume measurement in step 4, and then
calculate the [H2O] with urea added. Calculate ƒ in equation (7), the [urea] in the
solution, Keq in equation (6), and finally Δ G° from equation (5). The value for R is
0.00831 kJ/mole K.
8. Zamdot has repeated the measurements of urea and H2O (steps 2 to 4) for a total of 3
trials so you can make sure the data has good precision. Run through the calculations of
Keq and Δ G°.
9. Calculate an average ± average deviation value for Δ G°.. What does the sign of Δ G°
suggest?

Part III. Entropy Calculations

1. Use the average ΔH° and Δ G° values in The Gibbs-Helmholtz equation (1) to calculate
and average ΔS° value. Also, incorporate your ± values to calculate the precision for
ΔS°. What is the significance of the sign for ΔS°? (ΔS° values are usually listed as
J/mole K.)
 THERMODYNAMICS OF THE UREA-WATER SYSTEM
Lab section ___________________ Name____________________
Part I. Enthalpy Measurements
1 2 3

Mass water, g 30.14 30.05 30.10

Mass urea, g 1.80 1.80 1.80

Tinitial, °C 22.01 22.02 22.10

∆ T, °C 18.58 18.66 18.70

(MH2O) (CH2O) (∆T)

(Murea) (Curea) (∆T)

QR

∆ H°

Average ∆H°

Average Deviation

What is the Average ∆H°, _______________

Is this reaction endothermic or exothermic? _____________
Part II. Free Energy Measurements ∆ G° = - RT In Keq
1 2 3

Solution volume, mL 4.60 4.69 5.11

Mass H2O, g 2.907 3.101 3.310

Moles H2O

[H2O] in urea solution

ƒ = [H2O] urea sol’n

[H2O] pure
Mass urea, g 2.06 2.01 2.28

[urea]

Keq= [urea]
ƒH2O
∆G°

Average ∆G° XXXXXXX XXXXXXX

Average Deviation XXXXXXX XXXXXXX

What does the sign of ∆G° suggest?(is it spontaneous?)

Part III. Entropy Calculations Knowing ∆G° = ∆H° - T ∆S°
Rearrange the equation to solve for ∆S°(show your work)

What units should ∆S° have? _______________

∆S° value _______________________________________

What significance of the sign ∆S°?____________________________________

Is this reaction spontaneous or none spontaneous. Based on your data is there a temperature
where the spontaneity would change? _________________( from spontaneous to
nonspontaneous or non spontaneous to spontaneous) If you say yes, what would the temperature
be?