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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.

Assistant Coordinator Assistant

Known by :

Responsibility Lectuter

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

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.

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

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

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