DATE: 15/01/2017

EXPERIMENT NO: 06
EXPERIMENT: KONETICS OF OXIDATION OF FORMIC ACID BY BROMINE: A PPOTENTIOMETRIC
STUDY.
Aims & objectives
 Determination of kinetic parameters for the reaction HCO2H + Br2→ CO2 + 2H+ + Br –
 To become familiar with the use of potentiometric measurement for studying kinetics
of chemical reactions.
 To provide an opportunity,
o To construct an electrochemical cell using a reference
electrode and a redox electrode.
o To measure e.m.f of a cell using a digital voltmeter for the
purpose of obtaining measurement of concentration of an
electro active species.
o Use of the concentration to obtain kinetic parameters
relevant to a redox reaction producing electro active
species.
INTRODUCTION & THEORY
Bromine oxidize formic (methanoic) acid to carbon dioxide according to the following
stoichiometric equation,
HCO2H + Br2→ CO2 + 2H+ + Br –
In this experiment you will found the order of this reaction with respect to formic acid,
bromine and H+. The progress of the reaction is monitored electrochemically. The reaction
take place in an electrochemical cell whose voltage (or electromotive force, EMF) depends
on the concentration of bromine and bromide. This is very convenient way of following the
reaction as all we have to do this to read the EMF from a voltmeter (with high input
impedance) as a function of time.
The electrochemical cell has two electrodes.one electrode is simply a piece of platinum which
dips into the solution. The equilibrium reaction that takes place at this electrode is the
reaction of bromine to bromide.
Br2 + 2e ⇋ 2Br –………….(1)
The second electrode is a calomel electrode which consists of mercury metal in contact with
a paste made from insoluble Hg2Cl2, all surrounded by a saturated solution of KCl. The
equilibrium reaction which takes place at this electrode is
Hg2Cl2(S) + 2e ⇋ 2Hg (l) + 2Cl –………….(2)
The saturated KCl solution is held in a glass container around the Hg and Hg 2Cl2 a small
porous plug allows electrical contact between any solutions that the calomel electrode is
dipped into and the KCl solutions, but mixing of the two is inhibited.
The EMF of a cell consisting of the calomel electrode and the platinum electrode dipping
into a solution containing Br – and Br2 depends on the concentration of all the species
involved in the two electrode reactions, Eqns. [1] and [2]. The calomel electrode is in
electrical contact with the solution, but the contribution of the electrode to the EMF
remains constant as all of the species in not change.in this experiment we arrange for the
Br – ions to be in such large excess “that their concentration is unchanged during –
experiment. Thus, any change in the EMF of the cell is attributable solely to changes in the
concentration of Br2
The relationship between the cell EMF, E, and the concentration of Br2, [Br2], can be
shown to be,
𝑅𝑇
E = constant+ ln [Br2]………. (3)
2𝐹
[Constant=Formal potential]
Where R is the gas constant, T is the absolute temperature and F is the Faraday constant.
We are simply, using the EMF as an indicator of the concentration of bromine.
The relationship of equation (3) holds provide that the cell is not producing any current.
Simple voltmeter does not draw a significant current in making a measurement, however
modern electronic voltmeters draw currents of only a few nA. By using such an
instrument we can approach close to the ideal solution of measuring the voltage without
drawing a current.
We will assume that the rate law can be written as,
Rate=k [HCOOH]a [Br2]b [H+]c
Where a, b, and c are the orders with respect to formic acid, bromine and H+ respectively.
The aim of the experiment is to determine these orders.
As was explained above, an electrochemical cell essentially enables us to measure the
concentration of bromine, so it is convenient to express the rate in terms of the rate of
loss of bromine. Using calculus the rate law can be expressed as,
𝑑
[Br2] = -k [HCOOH]a [Br2]b [H+]c………… (4)
𝑑𝑡
The minus sign in equation (4) is to account for the fact that the reaction proceeds the
concentration of bromine falls. To simplifyt5he kinetics we make up reaction mixture in
which formic acid and H+ are in such large excess compared to bromine to bromine so
that their concentration remains essentially constant throughout the reaction.
The rate law can then be written
𝑑
[Br2]=-kapp[Br2]b where; kapp=[HCOOH]ainitial[H+]cinitial
𝑑𝑡
Kapp is the apparent rate constant called such, because it is not really a true rate constant
as its value depends on the initial concentrations of formic acid and H+.in the first part of
the experiment we test the hypothesis that the order with respect to bromine is one, i.e.
b=1

Confirmation of the order with respect to Br2 is ONE

If this the case then the rate law can be integrated as follows
𝑑
[Br2] = -kapp[Br2]
𝑑𝑡
1
∫ [𝐵𝑟 d [Br2]=∫ −kapp dt
2]
ln[Br2]=-kapp+A………. (5)
Where A is the constant of integration. The form of equation (5) tells us that, if the
reaction is first order in Br2, a plot of ln [Br2] against t, should give a straight line with
slope –kapp. We should already see above,
(Equation (3), that the cell EMF is directly proportionl to in [Br2])
𝑅𝑇
E = constant+ ln [Br2]
2𝐹
2FE = (constant⨯2F) + RT [Br2]
2𝐹𝐸−2𝐹𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
= ln [Br2]
𝑅𝑇
This can be arranged to give
2𝐹𝐸 2𝐹
ln [Br2] = - (constant)
𝑅𝑇 𝑅𝑇
And this expression for ln [Br2] is then substituted into equation (5) to give

2𝐹𝐸 2𝐹
- (constant) = -kapp+A
𝑅𝑇 𝑅𝑇
This equation can be tidied up to the simple from
𝑅𝑇
E = -kapp( )t + B………….. (6)
2𝐹

Where B is a constant at given temperature.

Determination of the order w.r.t H+ and formic acid
The second part of the experiment is to determine the orders with respect to [H+] and
formic acid this is done by the varying the initial concentration of these two species(still
keep them in excess, though) and then determining kapp. By comparing values ok kapp
determined for reaction mixtures with different concentrations of one species and the
same concentration of the other we can determine the order with respect to each in the
following way.
For a particular reaction mixture, let the initial concentration of formic acid be
[HCOOH]initial and the initial concentration of H+ be [H+]initial. The apparent rate constant,
kapp, is thus
Kapp=k[HCOOH]ainitial[H+]cinitial
Taking natural logarithms of both sides gives
ln kapp = ln k+ a ln {(HCOOH)initial+ c ln (H+)initial}………… (7)
This relationship implies that if kapp ios measured for a series of reaction mixtures with
different values of [HCOOH]initial but the same value of [H+]initial, a plot of ln kapp against ln
[HCOOH]initial will have slope a, the order with respect to formic acid. Likewise for a series
of reaction mixtures with different values of [H+]initial, but ths same value of [HCOOH]initial
plot of ln kapp against ln[H+]initial will have slope c, the order with respect to H+.
In this experiment we will determine the kapp for six different reaction mixtures, enabling
to obtain kapp for three different initial concentrations formic acid and the same of H+.
PROCEDURE
50.00 cm3 of the Br2 + NaBr solution was pipetted into a clean 150 cm3 tall-form beaker.
The beaker was placed on the stirrer and with a thermometer, the calomel electrode and
the platinum electrode dipped into the solution (the end of the calomel electrode only
needs to be just immersed). Electrodes and thermometer were clamped lightly using
retort clamps which can themselves be attached to the bench rack. The stirrer was going
gently.
The platinum electrode was connected to the positive terminal on the voltmeter and the
calomel electrode was connected to the negative terminal. When we were found that the
voltage is about 0.8v move onto making the kinetic runs.
The initial voltage was recorded from the cell. The content of the flask was added to the
beaker, stat the stopwatch and commence the voltage at 1 minute intervals until the
voltage has dropped by about 0.03v from its starting value of after 10 minutes, whichever
is the sooner.
Description of kinetic runs
For each run the Br + NaBr solution is put into the beaker and the cell set up as above.
The formic acid, HCl and distilled water are pre-mixed in a 50 cm3 volumetric flask. As
the total volume of this mixture is always 50 cm3 all we need to do is measure the HCl
acid and formic acid into the volumetric flask and then make it up to the line with distilled
water. Stopper the flask and invert it a few times to mix the contents.
The reaction is initiated by pouring the contents of volumetric flask into the cell. The
voltage is then read off as the reaction proceeds. As the reaction is first order it is not
necessary to start the stopwatch at the precise time of mixing (which is ill-defined in any
case). Start the stopwatch once you have added all of pre-mixed solution.
RESULTS
1st set 2nd set 3rd set 4th set 5th set 6th set
voltage/v voltage/v voltage/v voltage/v voltage/v voltage/v
Initial 0.805 0.798 0.797 0.812 0.808 0.804
voltage/v
Time/min
01 min 0.795 0.794 0.794 0.807 0.803 0.797
02 min 0786 0.791 0.792 0.801 0.796 0.789
03 min 0.776 0.787 0.790 0.796 0.789 0.781
04 min 0.766 0.782 0.788 0.790 0.783 0.774
05 min 0.756 0.778 0.786 0.785 0.777 0.766
06 min 0.746 0.774 0.784 0.779 0.770 0.759
07 min 0.735 0.770 0.782 0.774 0.764 0.751
08 min 0.725 0.765 0.780 0.769 0.758 0.744
09 min 0.713 0.761 0.777 0.764 0.752 0.736
10 min 0.697 0.757 0.774 0.759 0.746 0.728
Average 0.749 0.775 0.784 0.782 0.773 0.762

CALCULATIONS
𝑅𝑇
E = -kapp( )t + B
2𝐹
↓ ↓ ↓
Y= m x+c

𝑅𝑇
Gradient (m) = -kapp ( )
2𝑃
(𝑦1 −𝑦2 ) 2𝐹
Kapp = -
(𝑋1 −𝑋2 )
⨯ 𝑅𝑇
 Gradient (m) (⨯10 – 4) Kapp (⨯10 – 4) Vs -1 lnKapp
-1.73 13.47 -6.60
-9.80 17.63 -4.94
-5.00 38.97 -5.54
-7.70 60.00 -5.11
-9.16 71.39 -494
-9.58 74.66 -4.98

Plot of ln kapp vs ln[H+]initial for constant [HCOOH]initial

ln kapp [H+]initial ln[H+]initial
-6.60 0.05 -2.99
-6.94 0.12 -2.12
-5.54 0.25 -1.39
𝑥̅ = -6.36 𝑦̅= -2.16

Plot of ln kapp vs ln[HCOOH]initial for constant [H+]initial

ln kapp [HCOOH]initial ln[HCOOH]initial
-5.11 0.12 -2.12
-4.94 0.16 -1.83
-4.84 0.22 -1.51
𝑥̅ = -4.98 𝑦̅= -1.82

ln kapp = c ln{[H+]initial} + ln k + a ln {[HCOOH]initial}

y =m x + c
Gradient of ln kapp vs ln [H ] initial graph
+

(−5.44)−(−6.28)
m=
(−1.3)−(−2.1)
= 0.95
Therefore the order with respect to H+= 1

ln kapp = c ln{[HCOOH]initial} + ln k + a ln {[H+]initial}

y =m x + c
Gradient of ln kapp vs ln [HCOOH] initial graph
(−4.70)−(−5.10)
m=
(−1.42)−(−2.10)
= 0.5
Therefore the order with respect to HCOOH= 1
Discussion
Potentiometric methods of analysis are based on measuring the potential of
electrochemical cells without drawing appreciable current. The equipment required for
direct potentiometric measurements includes an ion-selective electrode, a reference
electrode and a potential measuring device. Conversional volumetric cannot be used
because only very small currents can be drawn. The reference electrodes should provide
a highly stable potential for an extended period of time.
Accuracy of ‘a’ and ‘c’ values can be increased by conducting this is a graphical methods,
more values will increase the accuracy of the calculation.
The most widely used reference electrode, due to its one of preparation and constancy
of potential, is the calomel electrode. Calomel electrode is a type of half-cell in which the
electrode is mercury coated with calomel (Hg2Cl2) and the electrolyte is a solution of
potassium chloride and saturated calomel. The saturated KCl solution is held in a glass
container around the Hg and Hg2Cl2 a small pours plug allows electrical contact between
any solutions is inhibits. The potassium chloride solution is used of define concentration.
This may be 0.1 M, 1M or saturated. These electrodes are referred to as the decimolar.
The molar and the saturated calomel electrode (S.C.E) and have the potentials. Relative
to the standard hydrogen electrode at 25Ċ, of 0.3358. 0.2534 And 0.244 volt of these
electrodes the S.C.E is most commonly used, largely because of the suppressive effect of
saturated potassium chloride solution on liquid junction potentials.