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APPROVAL SHEET

Complete report of Physical Chemistry II experiment entitle “Arrhenius


Equation and Activation Energy” that arranged by :
Group : III (Three)
Class : ICP A of Chemistry
It has been checked by assistant and assistant coordinator. So, this report is
accepted.

Makassar, January 2016


Assistant Coordinator Assistant

Hardianti Sahib Hardianti Sahib

Known by :
Responsibility Lectuter

Diana Eka Pratiwi, S.Si, M.Si


ID. 198006142008012016
A. TITLE OF EXPERIMENT
Arrhenius Equation and Activation Energy
B. OBJECTIVES
After done this experiment, the student be able to :
1. Explain about the reaction rate and temperature relationship
2. Determine the reaction rate constant
3. Calculate activation energy (Ea) using Arrhenius equation
C. LITERATURE REVIEW
Rate constants depend strongly on temperature, typically increasing rapidly
with increasing T . A rough rule, valid for many reactions in solution, is that, near
room temperature, k doubles or triples for each 10°C increase in T. In 1889
Arrhenius noted that the k(T) data for many reactions fit the equation :
k = Ae-Ea/RT
where A and Ea are constants characteristic of the reaction and R is the gas
constant. Ea is the Arrhenius activation energy and A is the pre-exponential factor
or the Arrhenius A factor. The units of A are the same as those of k. The units of
Ea are the same as those of RT, namely, energy per mole; Ea is usually expressed
in kJ/mol or kcal/mol (Levine, 2009 : 541).
The activation energy of the reaction is the up arrow from A to [B].
A→[B]→C
Viewed only from the enthalpy point of view, this is a non spontaneous process. If
the activation enthalpy to get to [B] is supplied, the reaction takes place and
the enthalpy change from [B] to C more than repays the enthalpy debt
incurred in production of [B]. The enthalpy hill from A to [B] is the activation
barrier (Rogers, 2011 : 157).
With very few exceptions the rate of reaction increases (often very sharply)
with increase in temperature. The relation between the rate constant k and
temperature was first proposed by Arrhenius:
k = Ae-E*/RT
The constant A is called the frequency factor, or pre-exponential factor; E* is the
activation energy. Converting equation to logarithmic form, we have:
E∗
log10 k = log10 A – 2303 RT

it is apparent that by determining the value of k at several temperatures, the plot of


logl0 k versus 1/T will yield the activation energy from the slope of the curve and
the frequency factor from the intercept. Although the frequency factor may
depend slightly on the temperature, unless the temperature range is very great, this
effect can ordinarily be ignored. The determination of the activation energy is an
important objective of any kinetic investigation (Castellan, 1983: 813).
It is found experimentally for many reactions that a plot of ln k against 1/T
gives a straight line. This behaviour is normally expressed mathematically by
introducing two parameters, one representing the intercept and the other the slope
of the straight line, and writing the Arrhenius equation :
Ea
ln k = ln A - RT

The parameter A, which corresponds to the intercept of the line at 1/T=0 (at
infinite temperature) is called the pre-exponential factor or the ‘frequency factor’.
The parameter Ea, which is obtained from the slope of the line (−Ea/R), is called
the activation energy. Collectively the two quantities are called the Arrhenius
parameters (Atkins, 2006 : 807).
The Arrhenius equation holds rather well for nearly all elementary
homogeneous reactions and for most composite reactions. A simple interpretation
of is that two colliding molecules require a certain minimum kinetic energy of
relative motion to initiate the breaking of the appropriate bonds and allow new
compounds to be formed. (For a unimolecular reaction, a certain minimum energy
is needed to isomerize or decompose the molecule; the source of this energy is
collisions. Note that a low activation energy means a fast reaction and a high
activation energy means a slow reaction. The rapid increase in k as T increases is
due mainly to the increase in the number of collisions whose energy exceeds the
activation energy. In the Arrhenius equation both A and Ea are constants.
Sophisticated theories of reaction rates yield an equation similar, except that A
and Ea both depend on temperature. When Ea ≫ RT (which is true for most
chemical reactions), the temperature dependences of Ea and A are usually too
small to be detected by the rather inaccurate kinetic data available, unless a wide
temperature range is studied (Levine, 2009 : 543).
The quantitative relationship between the reaction rate constant and
temperature is :
k = ae-Aa H/RT
This can be appreciated by looking at a Boltzmann distribution of reactant
molecules. The area under the Boltzmann curve that surpasses the activation
barrier at r increases sharply (exponentially) with temperature, leading to the
observed exponential increase in k. The exponential relationship between k and T
is called the Arrhenius rate law. The exponential relationship between k and T is
called the Arrhenius rate law. The number of activated molecules rises
exponentially with temperature (Rogers, 2011 : 157-158).
Activation energy is an energy minimum that must through of a reaction.
For example A → product.

Relationship between energy and reaction rate


In the A reaction be a product, Ea is the energy disturb that must solving by A
reaction. A molecule in case produce energy with do the collision success though
the activation energy (Ea). The collision occur between two molecules that
different, such as A and B (bimolecular reaction), disturb energy A and B forming
active complex (Tim Dosen Kimia Fisik II, 2015 : 6).
However, within the bounds of these limitations, the use of these screening
procedures invariably results in a well designed, efficient experiment, the outcome
of which can be supported with statistical significance. Thus, Plackett-Burman
design has been recommended for preformulation compatibility studies. In this
study, ascorbic acid syrup was developed and its stability was predicted by
Arrhenius equation. A Plackett-Burman experimental design was used to
investigate the compatibility of ascorbic acid (Sungthongjeen, 2004).
The heterogeneity of a solid surface is described by the distribution of
activation energies for the exchange reaction between gaseous and chemisorbed
molecules. The distribution, p (E), is defined in such as manner that p (E) dE is
the function of adsorption sites having an activation energy between E and E +
dE. It is assumed that for each value of the activation energy, E, there exists at any
given temperature a corresponding value of the exchange reaction rate constant,
k = ko e-E/RT
this assumption is correct if ko is either a constant or a function of T and E only :
ko = f (E, T)
ko is assumed to be a constant by most investigators. In this instance becomes the
Arrhenius equation (Brundgede, 1963).
D. APPARATUS AND CHEMICALS
1. Apparatus
a. Test tube (20 pieces)
b. Test tube rack (1 piece)
c. Thermometer 110°C (2 pieces)
d. Beaker glass 600 mL (1 piece)
e. Beaker glass 1000 mL (1 piece)
f. Graduated cylinder 10 mL (2 pieces)
g. Drop pipette (5 pieces)
h. Stopwatch (5 pieces)
i. Spray bottle (1 piece)
j. Tripod (1 piece)
k. Bunsen burner (1 piece)
l. Graduated cylinder 25 mL (1 piece)
m. Smooth rag (1 piece)
n. Rough rag (1 piece)
o. Test tube clamp (1 piece)
p. Beaker glass 250 mL (2 pieces)
2. Chemicals
a. Starch solution 3 % (C6H10O5)n
b. Diammonium bisulphate 0,04 M ((NH4)2S2O8)
c. Sodium thiosulphate solution (Na2S2O3)
d. Potassium iodide (KI)
e. Aquadest (H2O)
f. Matches
g. Ice cube
h. Tissue
E. PROCEDURES
1. Prepared the system
a. System I : ((NH4)2S2O8 2,5 mL was added into test tube I and also 2,5 mL of
H2O. 5 mL of KI was added into test tube II and also 0,5 mL Na2S2O3 and starch 3
% 0,5 mL.
b. System II : : ((NH4)2S2O8 3,5 mL was added into test tube I and also 1,5 mL of
H2O. 4 mL of KI was added into test tube II and also 1 mL of H2O, 0,5 mL
Na2S2O3 and starch 3 % 0,5 mL.
2. Both of the test tubes in the system I were put into ice cube in beaker 600 mL
until the temperature is same (both of the temperature 20°C).
3. The content of the both test tubes were mixed by content of 1st was filled into
2nd test tube and then filled again in the 1st tube.
4. The stopwatch is switched on, the time was measured but until blue color
appeared and full blue appeared.
5. The procedure was repeated for system II and for a temperature of 30°C, 40°C,
50°C, and 60°C.
F. OBSERVATION RESULT
Average Time 1 1
No System T (K) (K-1) ln
T t
Temperature (°C) (s)
1 System I 20 8320 293 3,413 × 10-3 -9,026
System II 20 7150 293 3,413 × 10-3 -8,875
2 System I 30 7020 303 3,333 × 10-3 -8,857
System II 30 6718 303 3,333 × 10-3 -8,813
3 System I 40 5630 313 3,195 × 10-3 -8,636
System II 40 5120 313 3,195 × 10-3 -8,462
4 System I 50 4730 323 3,096 × 10-3 -8,462
System II 50 4320 323 3,096 × 10-3 -7,762
5 System I 60 2350 333 3,003 × 10-3 -7,586
System II 60 1970 333 3,003 × 10-3 -7,586

G. DATA ANALYSIS
Ea
ln k1 = ln A - RT2
Ea
ln k2 = ln A - RT1
Ea Ea
ln k2- ln k1 = - RT2 + RT1
k2 Ea 1 1
ln k1 =- (T2 - T1)
R
Ea 1 1
ln k1- ln k2 = (T2 – T1)
R

1. 1st system
a. known : ln k1 = -8,857
ln k2 = -9,026
1
= 3,333 × 10-3
T1
1
= 3,413 × 10-3
T2

Question : Ea = …?
Problem solving :
Ea 1 1
ln k1- ln k2 = (T2 – T1)
R
Ea
-8,857-(-9,026) = (3,413 × 10-3 - 3,333 × 10-3) K
8,314J/mol K
Ea
0,169 = 8,314J/mol K (8 × 10-5 K-1)
1,405 J mol−1 K−1
Ea = 8 × 10−5 K−1

= 17563,325 J/mol
= 17,563 kJ/mol
b. Known : ln k1 = -8,636
ln k2 = -8,857
1
= 3,195 × 10-3
T1
1
= 3,333 × 10-3
T2

Question : Ea = …?
Problem solving :
Ea 1 1
ln k1- ln k2 = (T2 – T1)
R
Ea
-8,636-(-8,857) = (3,333 × 10-3- 3,195 × 10-3) K
8,314J/mol K
Ea
0,221 = 8,314J/mol K (1,38 × 10-4 K-1)
1,837 J mol−1 K−1
Ea = 1,38 × 10−4 K−1

= 13311,594 J/mol
= 13,311 kJ/mol
c. Known ln k1 = -8,462
ln k2 = -8,636
1
= 3,096 × 10-3
T1
1
= 3,195 × 10-3
T2

Question : Ea = …?
Problem solving :
Ea 1 1
ln k1- ln k2 = (T2 – T1)
R
Ea
-8,462-(-8,636) = (3,195 × 10-3- 3,096 × 10-3) K
8,314J/mol K
Ea
0,174 = 8,314J/mol K (9,9 × 10-5 K-1)
1,447 J mol−1 K−1
Ea = 9,9 × 10−5 K−1

= 14616,616 J/mol
= 14,616 kJ/mol
d. Known ln k1 = -7,762
ln k2 = -8,462
1
= 3,003 × 10-3
T1
1
= 3,096 × 10-3
T2

Question : Ea = …?
Problem solving :
Ea 1 1
ln k1- ln k2 = (T2 – T1)
R
Ea
-7,762-(-8,462) = (3,096 × 10-3- 3,003 × 10-3) K
8,314J/mol K
Ea
0,7 = 8,314J/mol K (9,3 × 10-5 K-1)
5,820 J mol−1 K−1
Ea = 9,3 × 10−5 K−1

= 62580,645 J/mol
= 62,581 kJ/mol
e. Known ln k1 = - 9,026
ln k2 = -7,762
1
= 3,413 × 10-3
T1
1
= 3,003 × 10-3
T2

Question : Ea = …?
Problem solving :
Ea 1 1
ln k1- ln k2 = (T2 – T1)
R
Ea
- 9,026-(-7,762) = (3,003 × 10-3- 3,413 × 10-3) K
8,314J/mol K
Ea
-1,264 = 8,314J/mol K (-4,1× 10-5 K-1)
−10,509 J mol−1 K−1
Ea = −4,1× 10−5 K−1

= 25631,707 J/mol
= 25,63 kJ/mol
So, the average Ea in 1st system
17,563+13,311+14,616+62,581+25,631
Ea =( ) kJ/mol
5
133,702
= kJ/mol
5

= 26,740 kJ/mol
The graph of 1st system

y
0.0035

0.0034

0.0033
y = -0.0003x + 0.0008
1/T

0.0032
R² = 0.8868
y
0.0031
Linear (y)
0.003

0.0029
-9.5 -9 -8.5 -8 -7.5
In 1/t

From the curve


y2−y1
Slope : tan 𝜃 = x2−x1
−8,857−(−8,636)
= 0,003195−0,00333
−0,221
= −1,35 x 10−4 K

= 1633,037 K-1
Ea
1633,037 K= 8,314 J/mol K

Ea = 13610,326 J/mol
= 13,610 kJ/mol
2. 2nd system
a. Known ln k1 = - 8,813
ln k2 = -8,875
1
= 3,333 × 10-3
T1
1
= 3,413 × 10-3
T2

Question : Ea = …?
Problem solving :
Ea 1 1
ln k1- ln k2 = (T2 – T1)
R
Ea
- 8,813-(-8,875) = (3,413 × 10-3- 3,333 × 10-3) K
8,314J/mol K
Ea
0,062 = 8,314J/mol K (8× 10-5 K-1)
0,515 J mol−1 K−1
Ea = 8 × 10−5 K−1

= 6437,512 J/mol
= 6,437 kJ/mol
b. Known ln k1 = - 8,541
ln k2 = -8,813
1
= 3,195 × 10-3
T1
1
= 3,333 × 10-3
T2

Question : Ea = …?
Problem solving :
Ea 1 1
ln k1- ln k2 = (T2 – T1)
R
Ea
- 8,541-(-8,813) = (3,333 × 10-3- 3,195 × 10-3) K
8,314J/mol K
Ea
0,272 = 8,314J/mol K (1,38× 10-5 K-1)
2,261 J mol−1 K−1
Ea = 1,38 × 10−5 K−1

= 16384,058 J/mol
= 16,384 kJ/mol
c. known : ln k1 = - 8,371
ln k2 = -8,541
1
= 3,096 × 10-3
T1
1
= 3,195 × 10-3
T2

Question : Ea = …?
Problem solving :
Ea 1 1
ln k1- ln k2 = (T2 – T1)
R
Ea
- 8,371-(-8,541) = (3,195 × 10-3- 3,096 × 10-3) K
8,314J/mol K
Ea
0,17 = 8,314J/mol K (9,9 × 10-5 K-1)
1,413 J mol−1 K−1
Ea = 9,9 × 10−5 K−1

= 14272,727 J/mol
= 14,272 kJ/mol
d. known : ln k1 = -7,586
ln k2 = -8,371
1
= 3,003 × 10-3
T1
1
= 3,096 × 10-3
T2

Question : Ea = …?
Problem solving :
Ea 1 1
ln k1- ln k2 = (T2 – T1)
R
Ea
-7,586-(-8,371) = (3,096 × 10-3- 3,003 × 10-3) K
8,314J/mol K
Ea
-0,785 = 8,314J/mol K (9,3× 10-5 K-1)
6,526 J mol−1 K−1
Ea = 9,3 × 10−5 K−1

= 70177,312 J/mol
= 70,177 kJ/mol
e. known : ln k1 = - 8,857
ln k2 = -7,586
1
= 3,413 × 10-3
T1
1
= 3,003 × 10-3
T2

Question : Ea = …?
Problem solving :
Ea 1 1
ln k1- ln k2 = (T2 – T1)
R
Ea
-8,857-(-7,586) = (3,003 × 10-3- 3,413 × 10-3) K
8,314J/mol K
Ea
-1,289 = 8,314J/mol K (-4,1× 10-5 K-1)
−10,717 J mol−1 K−1
Ea = −4,1 × 10−5 K−1

= 26138,405 J/mol
= 26,138 kJ/mol
So, the average Ea in 2nd system
6,437+16,384+14,272+70,177+26,138
Ea =( ) kJ/mol
5
133,408
= kJ/mol
5

= 26,682 kJ/mol
The graph of 2nd system

y
0.0035

0.0034

0.0033
y = -0.0003x + 0.0007
1/T

0.0032 R² = 0.8339
y
0.0031
Linear (y)
0.003

0.0029
-9 -8.5 -8 -7.5
In 1/t

y2−y1
Slope : tan 𝜃 = x2−x1
−8,813−(−8,284)
= 0,003195−0,00323
−0,529
= −1,35 x 10−4 K

= 3918,519 K-1
Ea
Slope = - RT
Ea
3918,519 K= - 8,314 J/mol K

Ea = 32578,567 J/mol
= 32,578 kJ/mol