LW1

KINETICS OF THE REACTION BETWEEN THIOSULFATE AND

HYDROCHLORIC ACID. EFFECT OF TEMPERATURE

MATERIAL PRODUCTS
1 rack
Na2S2O3 0,1 M
2 test tubes
HCl 0,5 M
1 thermometer
1 250 cm3 beaker
3 burettes (shared) thermostatic bath

AIM & THEORETICAL BACKGROUND

In this practice, the partial orders of the reaction and the activation energy for this reaction
will be determined
Na2S2O3 + 2 HCl → H2SO3 + S + 2 NaCl

To determine the partial orders of reaction, the initial velocity method will be used. If
we define the rate of the reaction as the rate of appearance of sulfur, the kinetic equation
is the following:

d[S]
= k[Na 2 S 2 O 3 ] [HCl]
a b

dt

and for a finite and small time, ∆t, assuming that the amount of sulfur formed is small, it
can also be considered that the concentration of the reactants spent is small
and, therefore, that the concentration of Na2S2O3 and HCl has remained constant and
equal to the initial one:
 ∆[S]
= k[Na 2 S 2 O 3 ]o [HCl]o
a b

∆t

By studying how the rate of the reaction varies with the initial concentration of the
reactants, the partial orders and the total order of the reaction can be determined.

To measure the speed of the reaction, the time required for a certain [S] to form will be
determined, the same in all experiments, so that the reaction speed will be proportional to
1/∆t.

To determine the partial order with respect to each reagent, several experiments will be
carried out in which the initial concentration of one of them will be kept constant and that of
the other will be varied.

1. Determination of the partial order of the reaction with respect to HCl

If several experiments are carried out with the same [Na2S2O3]o

∆[S]
v= = k[Na 2 S 2 O 3 ]o [HCl]o = k´[HCl]0
a b b

∆t

where k´ = k [Na2S2O3]o a .
As in all experiments, the time to reach the same [S] is going to be measured,

1 k´[HCl]0
b

= = cte[HCl]0
b

∆t ∆[S]

If the order of reaction with respect to HCl is zero,

1
= cte
∆t

2. Determination of the partial order of the reaction with respect to Na2S2O3

Several experiments will be carried out in which [HCl]0 will be kept constant, whereby:
 ∆[S]
v= = k[Na 2 S 2 O 3 ]o [HCl]o = k´´[Na 2 S 2 O 3 ]0
a b a

∆t

If the partial order with respect to Na2S2O3 is unity, taking into account the experimental
conditions used and expressing the concentration of thiosulfate as a function of the volume
of this added, the following is obtained:
1
= cte1VNa2S2O3
∆t

Therefore, a representation of 1/∆t against V (Na2S2O3 ) will give rise to a straight line that
passes through the origin and whose slope will be cte1 .

3. Influence of temperature on the reaction rate. Calculation of the activation energy.

The activation energy value can be obtained by applying the Arrhenius equation:

k = Ae −Ea / RT
Ea
ln k = ln A −
RT

If we know the values of the speed constant at two temperatures, k1 and k2 , we can
estimate the value of the activation energy by applying the previous equation at both
temperatures:

k1 Ea  1 1
ln =  − 
k2 R  T2 T1 

In our case, we know the values cte1 and cte2 for two temperatures, but:
cte1 k 1
=
cte 2 k 2

So we can estimate the value of the activation energy for this reaction.
EXPERIMENTAL PROCEDURE
1. Determination of the partial order of the reaction with respect to HCl
To verify that the reaction rate does not depend on the HCl concentration, the following
experiments will be performed:

Test tube Exp 1 Exp.2 Exp.3

1) Na2S2O3 (cm3) 4 4 4
2) HCl (cm3) 4 3 2
H2O (cm3) 0 1 2

In all experiments [Na2S2O3]o = cte and what varies is [HCl]o .

To measure the speed of the reaction in each of the experiments, proceed as follows:
• A stain is made in the beaker with a glass pen.
• At a certain moment WHICH IS CAREFULLY RECORDED (zero time), the contents
of tube 2) are quickly poured into tube 1), shaking to homogenize the mixture.
• tube 1) with the mixture is placed on the stain as indicated in the figure:

• It will be noted that some turbidity appears which increases until the spot is not
visible through the test tube, at which point the time is again taken and carefully noted.

The time it takes to stop seeing the stain is the time that elapses until a certain
concentration of sulfur is reached, the same in all experiments, therefore, if the partial order
of the reaction with respect to HCl is zero, the The time it takes to stop seeing the spot in
the three experiments should be the same.
2. Determination of the partial order of the reaction with respect to Na2S2O3
The following experiments will be performed:
Test tube Exp.1 Exp.2 Exp.3 Exp.4 Exp.5
1) Na2S2O3 (cm3) 8 7 6 5 4
2) HCl (cm3) 2 2 2 2 2
H2O (cm3) 0 1 2 3 4

In all experiments [HCl] is the same and what varies is [Na2S2O3].

To measure the speed of the reaction in each experiment, proceed in the same way as in
section 1. To ensure that the conditions are identical in all experiments, use a beaker filled
with water at room temperature (temperature that we must write down ), and place the test
tube against the wall of the beaker so that the inclination is always the same.

Determine, graphically, the value of cte1 .

3. Influence of temperature on the reaction rate. Calculation of the activation energy.
To carry out this study, the following experiments are carried out in a beaker containing hot
water at 45 ºC . Before mixing the contents of tubes 1 and 2, they must be thermostatted
at said temperature, for which it is necessary to keep them inside the thermostatic bath
for 5 minutes.

Test tube Exp.1 Exp.2 Exp.3 Exp.4 Exp.5

1) Na2S2O3 (cm3) 6 5 4 3 2
2) HCl (cm3) 2 2 2 2 2
H2O (cm3) 2 3 4 5 6

• Determine, graphically, the value of cte2.

• Calculate the (approximate) value of the activation
energy.