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Experiment #2

Chemistry II Laboratory

Enthalpy and Entropy of Zinc with Copper Sulfate


{Adapted from CCLI Initiative Computers Used in Chemistry Laboratory Instruction
Enthalpy & Entropy of Zinc with Copper Sulfate, Amend, J., Montana State University,
Bozeman, MT, 2009.}
Objectives: To determine changes in enthalpy and entropy of the reaction of zinc with copper
sulfate by two methods: calorimetry (Experiment #1) and electrochemistry (Experiment #2). To
compare enthalpy values found by both methods.

Introduction: Thermodynamics is the study of energy changes that occur in chemical and
physical processes. The enthalpy and entropy changes of a system undergoing such processes
are interrelated by the change in free energy, G, according to the equation,
G = H - TS

(1)

The investigation focuses on the reaction


Zn (s) + CuSO4 (aq)

ZnSO4 (aq) + Cu (s)

(2)

G will be calculated from the H and S values obtained electrochemically. The validity of
the Equation (1) will be tested by comparing the value of H obtained electrochemically with the
value of H obtained calorimetrically for the same reaction.
The Electrochemical Method:
The electrochemical method offers simple and accurate means for the determination of
thermodynamic quantities. A simple electrochemical cell can be assembled with use of small
beakers and a convenient and easily constructed salt bridge. The galvanic cell is described
Cu(s)/CuSO4(aq) || Zn(s)/ZnSO4(aq)

(3)

The overall galvanic cell reaction is


Zn (s) + Cu+2 (aq)

Zn+2 (aq) + Cu (s)

(4)

and it is essentially the same as that taking place in the calorimeter.


The quantity of electrical energy, F, produced or consumed during the electrochemical reaction
is a constant measured per mole of electrons, and can be accurately measured. The free energy
change, G, of an electrochemical reaction is related to the voltage, E, of the electrochemical
cell by the equation
G = -n FE

(5)

where n = number of moles of electrons transferred in a redox reaction.


and
F = Faradays constant of 96,500 C/mole of electrons.
Combining equations (1) and (5), and dividing both sides by the constant n, we obtain a linear
relationship between the voltage change, DE, and the enthalpy and entropy changes at different
temperatures.
E = - H _ + T S
nF
nF

(6)

E = S (T) - H
nF
nF

(7)

or

By measuring voltage E, of our electrochemical cell, at several temperatures, we can obtain a


plot of the voltage versus temperature. Assuming that H and S remain constant over a small
temperature range, we can calculate the S and H from the slope and the intercept of the
straight line respectively.
slope = S _
nF

(8)

Y- intercept = - H_
nF

(9)

and

G can now be calculated by means of Equation (1). We can verify its value by using Equation
(5). Please note that in both cases, G must be calculated for the same temperature. If the
calculations are done for 298 K (25 C), we can also verify the experimental value of E for this
temperature by employing the Nernst equation (7)
E = E RT ln [products]
nF
[reactants]

(10)

where E is the standard potential measured at 25 C and is 1.100 V for the cell under
consideration. When concentrations of the ZnSO4 and CuSO4 solutions are equal, the log term
of the Nernst equation becomes zero. Under these conditions, the standard voltage, E , of the
cell is equal to the measured voltage, E.
Safety Precautions: Safety goggles must be worn in the lab at all times. Any skin contact by
chemicals should be washed immediately.

BEFORE PERFORMING THIS EXPERIMENT.


EACH GROUP WILL NEED A LAPTOP COMPUTER!!
Interfacing the Microlab Software and Hardware
PLEASE FOLLOW THESE INSTRUCTIONS CAREFULLY!!
MicroLab Software:
1. Attach the USB cable to your computer. The cable should also be plugged into the
MicroLab Interface. Turn the Microlab Interface on (on/off button is on the front side of
the interface on the right hand side).
2. Your computer (Windows 7, Vista or XP Pro operating system) should recognize the
USB connection as a plug and play device.
3. The MicroLab software is available on the course LMS website, it is also available on a
CD, if necessary see your TA. Run the Microlab Set Up Executable file to run the
software on your computer. Follow the directions of the set up file. Once Set Up is
complete a MicroLab shortcut icon should be on your desktop.
4. If the computer and MicroLab interface are not communicating, for example you cannot
open the program or the program is running in simulation mode, see the Special Note
below.
5. At this point you will need to create an experiment program by selecting certain sensors
and calibrating those sensors as needed.
Special Note: Resetting the USB Communications port assignment
If Microlab will not open correctly, First close the MicroLab program and then do the following:
1. Open Control Panel on your computer.
2. Select System
3. Select Hardware
4. Select Device Manager
5. Scroll down to Ports (COM and LPT)
6. Select USB
7. Select Port Setting
8. Select Advanced
9. Open the drop down menu of Com Port Number
10. Select the lowest available COM port for the USB connection. (COM 1 or 2 works best.)
11. Save this setting and exit.
12. Re-open MicroLab.
Creating a MicroLab Program: Once the MicroLab program opens it will ask for a
particular experiment. Choose MicroLab Experiment then click on OK. (At this point an
experiment name is not required.)

1. Once the MicroLab window opens then select Sensor so that it is highlighted blue
(shown below).

2. At bottom of the same screen click Add Sensor.


3. The add sensor window will open for you to select the sensor, appropriate units and
calibration as needed.

From the drop down menu, select thermistor. Then click on the CAT-5 A input so that it is
highlighted red as shown above. Make sure your actual Thermistor is plugged into the same
CAT-5 jack on the front panel of the MicroLab interface panel. In the Label window, type in
Temperature. Click next to calibrate.

4. Once the calibration is complete then next task is continued construction of your
program. Follow similar steps to record voltage vs. temperature, so that the voltage
measurement is on the y-axis and the temperature is on the x-axis. There is no need to
calibrate the voltage sensor.

5. Once both sensors are added, you can click and drag each sensor to the graph,
spreadsheet and digital window. The temperature sensor should be on the x-axis and
voltage on the y-axis of the graph. By doing this you can see the change in voltage with
temperature in real time on the graph and digital window, as well the data will be
recorded to a spreadsheet for later analysis. (See image below.)

6. Once the sensors are in place and the program is complete, click on File on the top
toolbar, then click save experiment. Give your experiment program a name, such as
DeltaG.
7. It is important that the program is saved on the computer hard drive and that you
remember the program name and location in order to complete the experiment.
Part II Electrochemistry
Materials:
Zinc and Copper metal strips
0.5 M Copper sulfate
0.5 M Zinc Sulfate
0.1 M Potassium Nitrate
Petri Dish
Set of 3 10 mL beakers
Forceps
Microlab Voltage Alligator Clips
DeltaG.exp Microlab Program
Waste Container

Procedure:
1. Create an ice/water bath with the pan provided. Take care to not add too much ice or
water to the bath as to upset or over flow into the electrochemical cells.
2. Place the ice bath with electrochemical cell on a hot plate do not turn the heat on yet!!
Let the set-up stand for 15 minutes until the temperature stabilizes.
3. Pour about 5 mL of 0.1 M potassium nitrate (KNO3) into the center well of the
electrochemical cell. Pour about 5 mL of 0.5 M zinc sulfate (ZnSO4) into one of the
outer wells and add about 5 mL of 0.5 M copper sulfate (CuSO4) into a second outer
well. Do not let any of the solutions mix, they should be separate uncontaminated
solutions.
4. With clean forceps, take a strip of filter paper and dip one end into the center beaker
containing the KNO3 and then place the other end of the filter paper into the well
containing the ZnSO4. Repeat this procedure for a second piece of filter paper with the
KNO3 and CuSO4. This creates a salt bridge for the galvanic cell.
5. With clean forceps, take a strip of zinc metal and sand it to clean the surface of an oxide
layers. Bend the zinc strip so that one end of the zinc metal is in the well of ZnSO4
solution and the remaining portion is bent over the edge of the electrochemical cell.
Repeat this step for a strip of copper metal with one end immersed in the cell containing
CuSO4 solution.
6. Fasten the thermistor temperature probe to the ring stand with a clamp and adjust the
temperature probe so that the tip is immersed in the center well containing the KNO3. It
is assumed that the temperature of all three wells will be very close throughout the
experiment. Let the entire system come to equilibrium.
7. Make sure the DeltaG.exp Microlab program is open and record the temperature.
Record the initial temperature in your lab notebook.
8. Attach the alligator clips to the metal strips and record the voltage reading. If a negative
value appears on the screen, then reverse the alligator clips. Disconnect the alligator clips
once you have recorded a positive voltage in your lab notebook.
9. This step should be done as quickly as possible. Reattach the alligator clips, turn on
the hot plate to high, click on Start to engage DeltaG.exp Microlab program to begin
recording values. {Prolonged connection of the wires will cause electric current to flow
through the cell. This discharge will result in changes in concentrations of the solutions.
Since the measured voltage depends on these concentrations, there will be an error in the
voltage readings.}
10. Stop recording data when the temperature reaches 40 C. Turn off the hot plate!!
Disconnect the alligator clips and carefully remove the electrochemical cell from the
water bath and hot plate.
11. Retain and clean the zinc and copper strips. Collect all other waste into the waste jar
provided.
Microlab Software manipulations:
If you are working on this data after lab, open Microlab and choose Simulate/Open File/Hand
Enter to look at your data. Once the program opens you must then open each individual file to
use the data collected.

To find T for each reaction:


Click on Select Domain in the graph area of the MicroLab screen. A magnifying glass should
appear as your mouse pointer. Choose the area of the initial linear portion of the data before
mixing occurred by click and dragging the magnifying glass over the area of the data points (this
can be repeated, so do not worry if you do not get the area you want the first time!). Once you
release the mouse, the area will be rescaled on the screen.
For the Initial Temperature:
Click on Analysis in the graph area. The next window is to confirm that the area you chose is
correct and any changes in the domain selection can be made here. Click on OK. When the
next window opens, choose First Order (Linear). The equation to the line will appear below
the graph. Record that equation or print that graph. Enter the time of mixing in seconds as the x
value and calculate the y value. That will be your initial temperature in Celsius.
For the Final Temperature:
Click on Zoom Out All and the entire graph will be shown again. Perform the same steps as
above except choose the linear portion of the plot after mixing where the temperature has leveled
off. . Enter the time of mixing in seconds as the x value and calculate the y value. That will be
the final temperature in Celsius. The difference between the two temperatures (T final T
initial) is T for the reaction.
Other manipulations:
1. Data can be saved and exported to other graphing programs, i.e., Excel, as a comma
separated text file. Click on File on the top toolbar and then click on Export Data As
and choose Comma-Separated- Value text file and provide a file name and save.
2. Graph properties can be changed by clicking on Graph on the top toolbar and clicking
on Graph Properties. The properties window will offer a selection of changes that
can be made to the presentation of the data.
3. Graphs from the MicroLab program can be printed directly by clicking on Graph on the
top toolbar and click on Print This Graph.

Post Laboratory Report: You will need the enthalpy value found from Experiment 1.
Electrochemistry:
1. The Microlab Spreadsheet displays the voltage values of the cell in volts and is the y-axis
values of the plot. The temperature readings in degrees Celsius must be converted to
Kelvin. The temperature in Kelvin and is the x-axis values. Export the data as a
Comma-Separated- Value text file or .csv file and import to Excel. Using Excel,
construct a plot of voltage vs. temperature in Kelvin and then apply a linear curve fit
through the data. Report the equation for the linear fit. Include a copy of the plot.
2. Using the linear curve fit equation, calculate S from the slope (S/nF ) and H from
the Y-intercept = - (H/nF ).

3. Using the entropy and enthalpy changes determined above, calculate G at 25 C.


4. Calculate G using Equation (5). Find the voltage, E, value at 25 C for your set of data.
5. Compare and discuss the values of H obtained by method 1 from Experiment 1 and
method 2 from Experiment 2.
6. Discuss experimental error for both methods. (Human error is not an acceptable answer.)