LAB WORK 1. CHEMICAL KINETICS.

CHEMICAL EQUILIBRIUM

Purpose
To study the factors affecting reaction rate and chemical equilibrium (concentration
of the involved substances and temperature)
Procedure
Safety
All of the acids used in this experiment (H2SO4 and HCl) can cause chemical burns.
In particular, concentrated H2SO4 is extremely dangerous! If any of these chemicals spill
on you, immediately rinse the affected area under running water and notify your
instructor. KMnO4 and FeCl3 are very strong oxidizers and they can cause dark
discolorations to appear on your skin. Dispose of all chemical waste in the porcelain
container
Materials and equipment
1) Solution A (0.002 N KIO3 (aq)), Solution B (0.02 N Na2SO3, H2SO4, starch); 2
small test tubes, 10-mL graduated cylinder, 5 50-mL beakers, wash battle; 2) 0.1 N
H2C2O4 (aq), 0.05 N KMnO4 (aq), concentrated H2SO4; 4 calorimeters, 8 test tubes, test
tube rack; 3) 0.01 N FeCl3 (aq), 0.01 N KCNS (aq), concentrated FeCl3 and KCNS, KCl
powder; 10-mL graduated cylinder, 50-mL beaker, 4 small test tubes, spatula, funnel; 4)
starch aqueous solution, iodine aqueous solution; 2 big test tubes, beaker with hot water
Part 1. Dependence of the reaction rate on concentration of the reactants
To observe the dependence of the reaction rate on the concentration of the reactants
we use reaction between potassium iodate (KIO3) and potassium sulphite (Na2SO3) in
the presence of sulfuric acid (H2SO4) and starch (indicator on molecular iodine). Final
reaction equation will be
2KJO3 + 5Na 2SO3 + H 2SO 4 ⎯⎯⎯ starch
→ J 2 + 5Na 2SO 4 + K 2SO 4 + H 2O
or in ionic form
2IO3− + 5SO32− + 2H + ⎯⎯⎯
starch
→ I 2 + 5SO 42− + H 2O
Iodine and starch will give blue color.
Experimental procedure
1. Prepare Solution B in 5 different concentrations. The concentration of
Solution A is staying constant during the experiment. To prepare Solution B:
1.1. Place 10 mL of the Solution B into 5 labeled beakers.
1.2. Add distilled water according to the Table 1.
2. Place 20 drops of Solution A into the test tube.
3. From beaker 1 place 20 drops of Solution B into other test tube.
4. Quickly pour together Solutions A and B in the test tubes and turn on the stop-
watch.
 5. As soon as the mixture turning blue turn off the stop-watch.
6. Record your observations in Table 1.
7. Repeat items 3–7 for the Solution B in the beakers № 2–8.
1
8. Calculate the relative reaction rate: vrel = , s −1.
τ
9. Fill in Table 1 and make the graph of the dependence of the reaction rate on the
concentration of the reactants. (Use Chapter “Graphing standards”.)

Part 2. Dependence of the reaction rate on the temperature

Table – Dependence of the reaction rate on the concentration of the reactants
V, mL
Beaker
Distilled CSolution B, N τ, s vrel, s–1
number Solution B
water
1 10 0 0.0200
2 10 5 0.0133
3 10 10 0.0100
4 10 15 0.0080
5 10 20 0.0066
To study the dependence of the reaction rate on the temperature we use redox
reaction between oxalic acid (C2H2O4) and potassium permanganate (KMnO4) in the
presence of sulfuric acid. Reaction equation will be
5C2 H 2O 4 + 2KMnO 4 + 3H 2SO 4 → 10CO 2 + 2MnSO 4 + K 2SO 4 + 8H 2O
or in ionic form
5C2 H 2O4 + MnO4− + 6H + → 10CO2 + 2Mn 2+ + 8H 2O
purple colorless
In acidic medium MnO −4 ion reduces to Mn2+ ion. Change of the oxidation state of
manganese (from +7 to +2) results in the change of the color solution. It changes from
purple ( MnO −4 ) to colorless (Mn2+).
Experimental procedure
1. Take 8 test tubes.
2. Place 20 drops of 0.1 N H2C2O4 into 4 test tubes.
3. Place 20 drops of 0.05 N KMnO4 into another 4 test tubes and then add 20 drops
of concentrated H2SO4.
4. Cool test tubes with prepared mixture (KMnO4 and H2SO4) under cool running
water to room temperature.
5. Place test tubes with H2C2O4 and test tubes with the mixture into 4 calorimeters
with the temperatures of 30, 40, 50, and 60 ºC.
6. Keep test tubes with the solutions in the calorimeters during 1–2 minutes.
 7. Add solution from test tube containing mixture (under 30 ºC) to the test tube
with H2C2O4. Do not leave the test tube with H2C2O4 from the calorimeter. Turn
on the stop-watch.
8. Measure time of the reaction. (Reaction will end when the solution becomes
colorless.)
9. Record your observations in Table 2.
10.Repeat items 7–9 for 40, 50, and 60 ºC.
1
10.Calculate the relative reaction rate: vrel = , s −1.
τ
11.Fill in Table 2 and make the graph of the dependence of the reaction rate on the
temperature. (Use Chapter “Graphing standards”.)
Table – Dependence of the reaction rate on the temperature
Experiment
t, ºC τ, s vrel, s–1
number
1 30
2 40
3 50
4 60
12.Calculate the temperature coefficient of the reaction γ in the range from 30–
v v v
40 ºC ( γ30−40 C = 40 C ), 40–50 ºC ( 50 C ), 50–60 ºC ( 60 C ) and its average
v30 C v40 C v50 C
value.
Part 3. Effect of concentration of the reactants (products) changes on the
system at equilibrium
The effect of applying stress to a chemical system at equilibrium will be explored
in this experiment. The equilibrium system to be studied is given below
FeCl3 + KCNS ⇌ Fe(CNS)Cl2 + KCl
pale yellow colorless deep red
By observation the color changes the direction of a particular shift may be
determined. Such shifts may then be explained by careful examination of the effect of
the applied stress as dictated by the Le Chatelier principle.
Experimental procedure
Note that solution volumes are approximate for all reactions below.
1. Place into 50-mL beaker 10 mL of 0.01 N FeCl3 and add 10 mL 0.01 N KCNS.
2. Place 5 mL of the prepared solution into 4 small test tubes.
3. The solution in the first test tube remains untouched. It is a control sample for
comparison with other test tubes.
4. Add 3–5 drops of the concentrated FeCl3 to the solution in the second test tube.
Record your observations in Table 3.
5. Add 2–3 drops of concentrated KCNS to the solution in the third test tube. Record
your observations in Table 3.
6. Add spatula of KCl powder to the solution in the fourth test tube. Shake the test tube.
Record your observations in Table 3.
Table – The effect of concentration changes to a chemical system at equilibrium
Shifts in
Depth of the color
Test tube number Adding substance reaction
changes
direction
1 – – –
2 FeCl3
3 KCNS
4 KCl

Part 4. Effect of temperature changes on the system at equilibrium

To study the effect of temperature change on the system at equilibrium we use the
reaction between molecular iodine and starch. The equilibrium system to be studied is
given below

I2 + starch ⇌ starch-iodine complex (Δ𝐻 < 0)

pale yellow blue

Experimental procedure
This experiment is carried out by your instructor. Record your observation.
Make the conclusions concerning the lab work and answer the questions given
below.
Questions and Problems
1. What is meant by the rate of a chemical reaction? Write the reaction rate
expressions for the following reactions in terms of the disappearance of the
reactants and the appearance of the products:
(𝑎) H2(𝑔) + 𝐼2(𝑔) → 2HI
(𝑏) 2H2(𝑔) + 𝑂2(𝑔) → 2H2 𝑂(𝑔)
− +
(𝑐) 5Br−(𝑎𝑞) + BrO3(𝑎𝑞) + 6H(𝑎𝑞) → 3Br2(𝑎𝑞) + 3H2 𝑂(𝑙)

2. The rate law for the reaction

NH +4( aq ) + NO 2(
−
aq ) → N 2( g ) + 2H 2 O ( l )
is given by v = k[ NH +4 ][ NO −2 ]. At 25 ºC, the rate constant is 3.0 · 10–4 M · s. Calculate
the rate of the reaction at this temperature if [ NH +4 ] = 0.26 M and [ NO −2 ] = 0.080 M.
3. Define activation energy. What role does activation energy play in chemical
kinetics? Write the Arrhenius equation and define all terms.
4. Given the same concentrations, the reaction
CO( g ) + Cl2( g ) → COCl2( g )
at 250 ºC is 1.50 · 103 times as fast as the same reaction at 150 ºC. Calculate the energy
of activation for this reaction. Assume that the frequency factor is constant.
5. For the reaction
NO( g ) + O3( g ) → NO 2( g ) + O 2( g )
the pre-exponential factor A is 8.7 · 1012 cm3mol–1s–1 and the activation energy is
63 kJ/mol. What is the rate constant for the reaction at 75 ºC?
6. The rate constants of some reactions double with every 10-degree rise in
temperature. Assume a reaction takes place at 295 K and 305 K. What must the
activation energy be for the rate constant to double as described?
7. The equilibrium concentrations for the reaction
CO( g ) + Cl2( g ) → COCl2( g )
are [CO] = 1.2 ·10–2 M, [Cl2] = 0.054 M, and [COCl2] = 0.14 M. Calculate the
equilibrium constant (KC).
8. The equilibrium constant KP for the reaction
NO( g ) + O3( g ) → NO 2( g ) + O 2( g )
is 158 at 1000 K. Calculate PO2 if PNO2 = 0.400 atm and PNO = 0.270 atm.
9. The equilibrium constant (KC) for the reaction
2NO( g ) + Cl2( g ) → NOCl( g )
is 6.5 · 104 at 35 ºC. in a certain experiment 2.0 · 10–2 mole of NO, 8.3 · 10–3 mole
of Cl2, and 6.8 moles of NOCl are mixed in a 2.0-L flask. In which direction will the
system proceed to reach the equilibrium. Write expressions for KC and KP.