CEAC 104 Son 3 Deney
CEAC 104 Son 3 Deney
CEAC 104 Son 3 Deney
GENERAL CHEMISTRY
Experiment 4
Heat of Neutralization
Prelaboratory Work
Before the experiment in the laboratory, you should be able to answer these questions.
1. Calculate the volume of solution of 1.50 M HNO3 required in part (A) of the procedure.
2. Calculate the mass of NH4NO3 required in part (B) of the procedure. Show your reasoning.
3. Explain in stepwise fashion (number the steps) how you will determine the ΔH of formation of
NH4NO3 from your data and information given in the experiment. Use actual numbers whenever
possible.
4. How many joules are required to change the temperature of 80.0 g of water from 23.3 °C to
38.8 °C?
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Theory
In chemical reactions, energy change is observed. This energy change is usually in the form of
heat and at constant pressure it is defined as heat of reaction or enthalpy change (ΔH). To form
1 mole of compound from its constituent elements, necessary amount of enthalpy change occurs
and this change is defined as enthalpy of formation. If heat is released during the reaction, ΔH is
shown with negative sign and the reaction is called exothermic reaction. If heat is absorbed
during the reaction, ΔH is shown with positive sign and the reaction is called endothermic
reaction.
Direct measurement of enthalpies of formation is difficult experimentally, so indirect methods
involving enthalpies of reaction are used. Hess’s Law states that the change in a thermodynamic
property such as enthalpy depends on the initial and final states and is independent of path
followed. An example for Hess’s Law is given below.
Assume that ΔH1 and ΔH2 are known. If first and second reactions are added, net reaction
becomes;
Given that ΔH1 = - 45.8 kJ/mol and ΔH2 = - 35.4 kJ/mol, we can calculate the ΔH formation of
NH3(aq) as -81.2 kJ/mol.
The heat is measured experimentally by allowing the reaction to take place in a thermally
insulated vessel called as calorimeter. If the calorimeter is perfectly insulated, no heat change
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occurs between system and surrounding and the system is defined as adiabatic (Q=0).
Consequently, at constant pressure, ΔHsystem is also equal to zero. The formulation of enthalpy
change of the system, ΔHsystem, is shown as in Equation (1).
ΔHsystem = ΔT (heat capacity of calorimeter + heat capacity of contents) (1)
For endothermic reaction in adiabatic system, Equation (1) can be written as below.
In a similar manner, for exothermic reaction in an adiabatic system, Equation (1) can be
simplified as:
ΔHsystem = -nΔHreaction + CpΔT
0 = -nΔHreaction + CpΔT
nΔHreaction = CpΔT
In this experiment, you will determine the heat of formation of various ammonium salts NH 4X(s)
where X is Cl, NO3 or SO4 by combining measurements of the heat for the neutralization
reaction;
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Materials
Procedure
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3. Add the acid solution to the NH3 and swirl to mix.
Continue taking temperature data at 30 seconds
intervals while swirling the solution occasionally.
PART B: Dissolving
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Calculations
1. Plot temperature versus time graph using your data and determine ΔH neut for (a) and ΔH diss for
(b).
2. Take ΔHf of 1.5 M NH3 as -81.2 kJ/mol and ΔHf of 1.5 M HCl as -165.1 kJ/mol, calculate the
ΔHf of NH4Cl(s).
3. Do the same calculations for NH4NO3(s) using -206.0 kJ/mol for the ΔHf of 1.5 M HNO3.
4. Calculate ΔHf of (NH4)2SO4 using -884.2 kJ/mol for the ΔHf of 1.5 M H2SO4. [ Note that all
ΔHf are per mol (not per 1.5 mol)]
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DATA SHEET
Heat of Neutralization
Student’s Name : Date:
Laboratory Section/Group No :
Assistant’s Name and Signature :
Prelaboratory Work
1. Volume of 1.5 M HNO3 solution:
2. Mass of NH4NO3:
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Results
1. Calculate ΔHneutralization:
2. Calculate ΔHdissociation:
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CEAC 104
GENERAL CHEMISTRY
Experiment 5
The Thermodynamics of Solubility of Potassium
Chlorate
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THEORY:
The solubility of KClO3 will be measured at various temperatures. From the molar solubility,
s: moles of solute per liter of solvent, a value of the solubility product constant, K sp, can be
calculated at various temperatures for the following reaction:
Ksp = [K+][CIO3-] = s2
The solubility of a solid is exponential with respect with temperature. A plot of the solubility
product constant, Ksp, vs temperature (K) will give an exponential curve.
The relationship between ΔHo and the Ksp comes from the free energy equations
(2) ΔGo = ΔHo - TΔSo , where ΔHo is the standard enthalpy change
and ΔSo is the standard entropy change.
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Both the molal heat of solution ΔH o and the entropy ΔSo values can be obtained for the
reaction by solving the equation relating the slope of the graph with ΔH o and the y- intercept with
ΔSo. The plot of ln K vs 1/T in K-1 will give the following equation of a straight line:
Each group will be assigned a different composition of solution to measure. The data from
each group will be combined and plotted.
SAFETY PRECAUTIONS
KClO3 is flammable and strong oxidizing agent. Therefore, dispose of all wastes by
flushing them down the sink with plenty of running water.
Avoid any contact between the KClO3 and paper.
REVIEW QUESTIONS:
Before beginning this experiment in the laboratory, you should be able to answer the following
questions:
1. Suppose a reaction has negative ΔH° and negative ΔS°. Will more or less product be
present at equilibrium as the temperature is raised?
2. Fisherman know that on hot summer days, the largest fish will be found in deep sinks in
lake bottoms, where the water is coolest. What is the reason of it, think about the
temperature dependence of oxygen solubility in water?
3. Nitrogen dioxide reacts with water to produce nitric acid according to following reaction:
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PROCEDURE:
1.In a test tube, weigh a sample of KClO3 to the nearest 0.01g. The amount of sample will range
from 1 to 5 grams in 1 gram increments.
2. Pipet 10 mL of distilled water into the test tubes. Stir the mixture with a glass rod.
3. Gently warm the mixture until the crystals dissolve. For high sample amounts, an evaporating
dish can be used as a water bath to transfer heat more evenly. Insert thermomer into test tube and
try to note the temperature at which the last crystals go into solution. Then allow the solution to
cool until crystals reappear and again note the temperature.
4. Record the saturation temperature you have just determined and enter your values in your data
sheet.
CALCULATIONS:
A. Ksp values.
1. Write the equation for the equilibrium between solid KClO3 and its ions in solution and the
expression for the Ksp of KClO3.
2. From the weight-volume data, calculate the molar concentration of KClO3 for each
composition. This is the molar solubility at the saturation temperature measured.
3. Calculate the solubility product of KClO3 for each trial. Use the concentrations found in step 1.
4. Tabulate the resulting values of solubility, Ksp, and temperature in your lab datasheet.
5. Using Excel, graph temperature (Kelvin) on the horizontal axis (x-axis) versus Ksp on the
vertical axis (y-axis).
1. Using excel calculate values of 1/T, the reciprocal of the absolute temperature, and ln Ksp for
each of the points graphed in part A.
2. Make a new graph with ln Ksp on the vertical axis and 1/T (K-1) on the horizontal axis. Use the
linear curve fit option in excel to obtain the best fit linear fit.
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3. From the slope of your graph calculate ΔHo, the heat of solution for KClO3
Also determine ΔS° from the y-intercept.
Tabulate data for the written report and include the curve fit equation with the graph of lnKsp vs
1/T.
QUESTIONS:
1. When a certain solid dissolves in water, the solution becomes cold. Is ΔH soln for this solute
positive or negative? Is the solubility of this substance likely to increase or decrease with
increasing temperature?
2. What is the value of equilibrium constant for a reaction for which ΔG°= 0? What will
happen to the composition of the system if we begin the reaction with the products?
3. The solubility of ZnS at 25oC is 3.5 x 10-12 M. What is the Ksp for ZnS? What is ΔG° at
25°C?
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DATA SHEET
The Thermodynamics of Solubility of Potassium Chlorate
A. Ksp Values
1. Write the reaction equation and the solubility product expression for KClO3.
2.
Amount of Molar Ksp T (°C) T (K)
KClO3 (g) Concentration of
KClO3 (mol/L)
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B. Molal Heat of Solution of KClO3
1.
2. Draw ln Ksp vs 1/T graph using Excel and calculate ΔH° from the slope and ΔS° from y-
intercept.
ΔH° =
ΔS° =
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CEAC 104
GENERAL CHEMISTRY
Experiment 6
Electrochemical Cells and Thermodynamics
Purpose: To examine the correlation between the reactions of metals and their ions (half cells), and
to measure the voltages produced at various concentrations when two half cells are combined to form
electrochemical (voltaic) cells. The voltage of the redox reactions will be calculated theoretically via
Nernst equation.
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THEORY:
Electrochemistry is that area of chemistry that deals with the relations between chemical
changes and electrical energy. It is primarily concerned with oxidation-reduction phenomena.
Chemical reactions can be used to produce electrical energy in cells that are referred to as voltaic,
or galvanic, cells. Electrical energy, on the other hand, can be used to bring about chemical
changes in what are termed electrolytic cells. In this experiment you will investigate some of the
properties of voltaic cells.
Oxidation-reduction reactions are those that involve the transfer of electrons from one
substance to another. The substance that loses electrons is said to be oxidized, while the one
gaining electrons is reduced. Thus if a piece of zinc metal were immersed into a solution
containing copper (II) ions, zinc would be oxidized by copper (II) ions. Zinc loses electrons and
is oxidized, and the copper (II) ions gain electrons anda re reduced. We can conveniently express
these processes by the following two half-reactions, which add to give the overall reaction:
______________________________________ [1]
In principle, any spontaneous redox reaction can be used to produce electrical energy- that is,
the reaction can be used as the basis of a voltaic cell. The trick is to seperate the two half
reactions so that electrons will flow through an external circuit. A voltaic cell that is based upon
the reaction in Equation [1] and that uses a salt bridge is shown in Figure 6.1.
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Figure 6.1 Complete and functioning voltaic cell using a salt bridge to complete the electrical
circuit.
The cell voltage, or electromotive force (abbreviated emf), is indicated on the voltmeter in
units of volts. The cell emf is also called the cell potential. The magnitude of teh emf is a
quantitative measure of the driving force or thermodynamic tendency for the reaction to occur.
In general, the emf of a voltaic cell depends upon the substances that make up the cell as well as
on their concentrations. Hence, it is common practice to compare Standard cell potentials,
symbolized by E0cell. These potentials correspond to cell voltages under Standard state
conditions-gases at 1 atm pressure, solutions at 1 M concentration and temperature at 25 0C.
Just as the overall cell reaction may be regarded as the sum of two half-reactions the overall
cell emf can be thought of as the sum of two half-cell potentials, that is, the sum of the voltage of
the oxidation half-reaction (Eox) and the voltage of the reduction half-reaction (Ered):
Because it is impossible to measure directly the potential of an isolated half-cell, the Standard
hydrogen half-reaction has been selected as a reference and has been assigned a standar reduction
potential of exactly 0.000 V:
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To demonstrate the consequence of this, let us consider a voltaic cell that utilizes the
following reaction:
The Standard cell emf of this cell is 0.76 V (that is, E 0cell = 0.76 V). Because the Standard
reduction potential of H+ is 0.000 V, it is possible to calculate the Standard oxidation potential,
E0ox, of Zn:
[2]
Thus the Standard oxidation potential of 0.76 V can be assigned to Zn. By measuring other
Standard-cell emf values, we can establish a series of Standard potentials for other half-reactions.
It is important to note that the half cell potential for any oxidation is equal in magnitude but
opposite in sign to that of the reverse reduction. Hence,
It is customary today to tabulate half-cell potentials as Standard reduction potentials and also
to refer to them as Standard electrode potentials.
EXAMPLE 1:
The cell in Figure 6.1 may be represented by the following notation:
The double bar represents the salt bridge. Given that E 0cell for this cell is 1.10 V and that E ox is
0.76 V for zinc (see Equation [2]), find the Standard electrode potential, E 0red, for the reduction of
copper ( .
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Solution 1:
The free-energy change, G, associated with a chemical reaction is a measure of the driving force
or spontaneity of the process. If the free-energy change of a process is negative, the reaction will
ocur spontaneously in the direction indicated by the chemical equation.
The cell potential of a redox process is related to the free-energy change as follows:
[3]
In this equation, F; is Faraday's constant, the electrical charge on 1 mol of electrons:
and n represents the number of moles of electrons transferred in the reaction. For the case when
both reactants and products are in their standard states, Equation [3] takes the following form:
The maximum amount of work that can be obtained from a galvanic cell is equal to the free energy
change, ΔG, for the process.
The standard free-energy change of a chemical reaction is also related to the equilibrium constant
for the reaction as follows:
where R is the gas-law constant (8.314 J/K mol) and T is the temperature in Kelvin. Consequently,
E° is also related to the equilibrium constant. From Equations [4] and [5] it follows that
When T = 298 K, In K is converted to log K, and the appropriate values of R and 9; are substituted,
Equation [6] becomes
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We can see from this relation that the larger K is, the larger the standard-cell potential will be.
In practice, most voltaic cells are not likely to be operating under standard-state conditions. It is
possible, however, to calculate the cell emf, E, under non-standard-state conditions from a
knowledge of E°, temperature, and concentrations of reactants and products:
Q is called the reaction quotient; it has the form of an equilibrium-constant expression, but the
concentrations used to calculate Q are not necessarily equilibrium concentrations. The relationship
given in Equation [8] is referred to as the Nernst equation).
Let us consider the operation of the cell shown in Figure 1 in more detail. Earlier we saw that the
reaction
Cu2+ + Zn Zn2+ + Cu
is spontaneous. Consequently, it has a positive electrochemical potential (E° = 1.10 V) and a
negative free energy (ΔG° = - nFE°). As this reaction occurs, Cu2+ will be reduced and deposited as
copper metal onto the copper electrode. The electrode at which reduction occurs is called the
cathode. Simultaneously, zinc metal from the zinc electrode will be oxidized and go into
solution as Zn2+. The electrode at which oxidation occurs is called the anode. Effectively, then,
electrons will flow in the external wire from the zinc electrode through the voltmeter to the copper
electrode and be given up to copper ions in solution. These copper ions will be reduced to copper
metal and plate out on the copper electrode. Concurrently, zinc metal will give up electrons to
become Zn2+ ions in solution. These Zn2+ ions will diffuse through the salt bridge into the copper
solution and replace the Cu2+ ions that are being removed.
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EXAMPLE 2:
Calculate the cell potential for the following cell:
Zn | Zn2+ (0.6 M) || Cu2+ (0.2 M) Cu
given the following:
Cu2+ + Zn Cu + Zn2+ E°=1.10V
(HINT: Recall that Q includes expressions for species in solution but not for pure solids.)
Solution 2:
You can see that small changes in concentrations have small effects on the cell emf.
A list of the properties of electrochemical cells and some definitions of related terms are given in
Table 6.1.
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Chemists have developed a shorthand notation for electrochemical cells, as seen in Example 1. The
notation for the Cu-Zn cell that explicitly shows concentrations is as follows:
Zn | Zn2+(xM) || Cu2+(yM) | Cu
Anode Cathode
(oxidation) (reduction)
In this notation, the anode (oxidation half-cell) is written on the left and the cathode (reduction
half-cell) is written on the right.
Your objective in this experiment is to construct a set of three electrochemical cells and to measure
their cell potentials. With a knowledge of two half-cell potentials and the cell potentials obtained
from your measurements, you will calculate the other half-cell potentials and the equilibrium
constants for the reactions. By measuring the cell potential as a function of temperature, you may
also determine the thermodynamic constants, ΔG, ΔH, and ΔS, for the reactions. This can be
done with the aid of Equation [9]:
ΔG may be obtained directly from measurements of the cell potential using the relationship
A plot of ΔG versus temperature in degrees Kelvin will give -ΔS as the slope and AH as the
intercept. A more accurate measure of ΔH can be obtained, however, by substituting ΔG and ΔS
back into Equation [9] and calculating ΔH.
REVIEW QUESTIONS:
Before beginning this experiment in the laboratory, you should be able to answer the following
questions:
1.Define the following: faraday, salt bridge, anode, cathode, voltaic cell, electrolytic
cell.
2.Write a chemical equation for the reaction that occurs in the following cell:
Ag | Ag+ || Cu2+| Cu.
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3. Given the following E°'s, calculate the standard-cell potential for the cell in
question 2.
E° = +0.34 V
E° = +0.80 V
4. Calculate the voltage of the following cell:
Zn | Zn2+ (0.10 M) || Cu2+ (0.40 M) | Cu
5. Calculate the cell potential, the equilibrium constant, and the free energy for the
following cell:
Ba(s) + Mn2+(aq)(l M) Ba2+(aq)(l M) + Mn(s)
given the following E° values:
E° = -2.90 V
E° = -1.18 V
6. Would you normally expect ΔH0 to be positive or negative for a voltaic cell?
Justify your answer.
7. Predict whether the following reactions are spontaneous or not.
Pd2++ H2 Pd + 2H+ Pd2+ + 2 Pd E° = 0.987 V
Sn4++ H2 Sn2++ 2H+ Sn4+ + 2 Sn2+ E° = 0.154 V
Ni2+ + H2 Ni + 2H+ Ni2+ + 2 Ni E° =-0.250 V
Cd2+ + H2 Cd + 2H+ Cd2+ + 2 Cd E° = -0.403 V
From your answers decide which of the above metals could be reduced by hydrogen.
8. Identify the oxidizing agents and reducing agents in the reactions in question 7.
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PROCEDURE:
Construct the apparatus shown in the Figure 6.1 with great care when installing the U-tube salt
bridge.
A. Cell Voltage
1. Pour about 150 mL of 0.5 M CuSO4 into a beaker. Bend a sand papered Cu strip
and hang over the side of the beaker so that it is partly immersed in the solution.
2. Clean a Zn strip by briefly immersing it in about 75 mL diluted HC1 in a beaker.
Do not let the strip remain for very long in the, HCl solution. Otherwise, it will
react liberating H2. (HCl cleans Zn by dissolving the surface layer exposing the
fresh metal.) Immediately rinse the Zn strip thoroughly in distilled water.
3. Bend the Zn strip and hang it over the side of the beaker containing 150 mL of
0.5 M ZnSO4.
4. Use the crocodile clips to connect the terminals of the multimeter to the metal
electrodes.
5. Construct the salt bridge as described above and immediately read the initial cell
voltage. Be certain that the clips make good contact with the metal strips. Record
this voltage and the temperature of the cells on your data sheet. If your measured
potential is negative, reverse the wire connection.
Record the voltage and temperature of each cell on your data sheet.
DO NOT MOVE any part of the cell, because the voltage will fluctuate if you do.
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The following points should be considered for the design of the experiment:
1. The effect may be investigated for only the cathode compartment solution instead
of both solutions.
2. Vary the concentration of reactants from 0.5 M to 0.25 M and 0.05 M to
determine the effects of concentration changes. Before coming to the laboratory,
make the necessary calculations for the design of the experiment in order to
observe significant changes in the cell potential.
3. Try to determine if the cell voltage varies in some regular way with concentration.
Is variation linear or exponential or whatever?
CALCULATIONS:
1. For each cell write the anode half reaction and the cathode half reaction.
2. For each cell measure the initial cell potential. Calculate the cell potential using
the Nernst equation and compare it with the measured value. What is the percent
error in your measurement?
3. Calculate the maximum work in Joule for the galvanic cell you constructed.
QUESTIONS:
1. Write the chemical equations that occur in the following cells;
Pb | Pb(NO3)2 || AgNO3 | Ag
Zn | ZnCI2|| Pb(NO3)2 | Pb
Pb | Pb(NO3)2 || NiCl2 | Ni
2. Which of the following reactions should have the larger ernf under standard
conditions? Why?
CuSO4(aq) + Pb(s) PbSO4(s) + Cu(s)
Cu(NO3)2(aq) + Pb(s) Pb(NO3)2(aq) + Cu(s).
3. Calculate ΔG for the reaction in Example 2.
4. Voltages listed in textbooks and handbooks are given as standard-cell potentials
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(voltages). What does a standard cell mean? Were the cells constructed in this
experiment standard cell? Why or why not?
5. As a standard voltaic cell runs, it "discharges" and the cell potential decreases with
time. Explain.
6. Using standard potentials given in the appendices, calculate the equilibrium
constants for the following reactions:
Cu(s) + 2Ag+(aq) Cu2+(aq) + 2Ag(s)
Zn(s) + Fe2+ (aq) Zn2+(aq) + Fe(s)
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DATASHEET
Electrochemical cells and Thermodynamics
Student's Name : Date:
Laboratory Section/Group No :
Assistant's Name and Signature :
Calculations:
Cathode half reaction:
T (°C):
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