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Physical Pharmacy
Lab - 4 -
Kinetics
Assistant Lecturer Ahmad A.Yosef
2018/2019
1Assistant Lecturer Ahmad A.Y
2
This lab is used to demonstrate the way at which the break down of
the product occurs at elevated temperature. which is used to forecast
the rate at which the activity deteriorates at temperature of storage &
thus to estimate the shelf life of the product ( Expire Date ) .
Kinetic
Assistant Lecturer Ahmad A.Y
3
*Kinetics:- is the studying of reaction rate & factors affecting it.
*Reaction rate:- is the velocity or the speed at which the reaction
proceed ,it is given by ± dc/dt ,this expression gives + the increase
or – the decrease of concentration dC within a given time interval dt.
*Reaction order:- is the number of atoms or molecules whose
concentration determine the reaction rate . the reaction order shows
the way of how the concentration Of reactant affecting the reaction rate
DEFINITIONS
Assistant Lecturer Ahmad A.Y
4
Factors that may affecting reaction rate:
1-
concentartion
of reactant
2-
temperature
3-catalysts
4-presence of
solvents
5-light
6-pH
Assistant Lecturer Ahmad A.Y
5
A-Zero order reaction:- the rate of reaction is independent on
reactant conc.
So , -dc/dt=k˳
B-First order reaction:- A→B+C
So - dc/dt=k[A]
C-Second order reaction:- A+B→C+D
So -dc/dt=k[A][B]
D-Third order reaction:- 2A+B→C+2D
So, -dc/dt=k[A]²[B]
Orders of reaction:
Assistant Lecturer Ahmad A.Y
6
*half life t 1/2% :- is the time required for the drug to decompose to
one half its original concentration .
*shelf life t 90%:- is the time required for the drug to lose10% of it's
original concentration .Or it’s the time required for the drug to degrade to
90% of it's original concentration.
Assistant Lecturer Ahmad A.Y
7
A-Zero order reaction:-

Assistant Lecturer Ahmad A.Y
8
B-First order reaction :-

Assistant Lecturer Ahmad A.Y
9
* To calculate t 50%
Log 0.5c˳ = log c˳ - kt ½ / 2.303
kt ½ /2.303 =logc˳ - log0.5c˳
kt ½ / 2.303= log c˳/0.5c˳
kt ½ /2.303=log2
t 1/2= 0.693/ k
*To calculate t 90%
Log 0.9c˳ = logc˳-kt /2.303
K t/2.303 =log c˳/0.9c˳
t 90% = 0.10% /k
Assistant Lecturer Ahmad A.Y
10
Both t1/2 & t90% are
concentration Independent ,
thus for t1/2 it takes the same
amount of time to reduce the
concentration of drug from
100mM to 50 mM as it does
from 50 mM to 25 mM.
Assistant Lecturer Ahmad A.Y
11
Temperature

 lnK = lnA – Ea/RT
→ 2.303 log K = 2.303 log A – Ea/RT
Log K = log A -Ea / 2.303 RT
Assistant Lecturer Ahmad A.Y
12
The plot known as Arrhenius plot for predicting stability
at room temperature.
Note:-Arrhenius found that speed of many reactions
increase about 2 or 3 time with each 10c˚rise in
temperature .
So we can apply Arrhenius equation to find the reaction
rate at temperature of storage.
Assistant Lecturer Ahmad A.Y
13
Aim of experiment:-
Studying the effect of temperature on the hydrolysis of aspirin (1st
order kinetic) in order to use it as guide to estimate t ½ and t 90%
Materials & equipment:-
Aspirin, Trisodium citrate, NaOH
Phenol red indicator ,0.2 N NaOH solution
Conical flask(250ml)&conical flask(150,50 cc),pipette& burette
three water baths.
Assistant Lecturer Ahmad A.Y
14
Procedure
 1- Prepare the following mixture in 250ml conical flask :
Aspirin 4.5 gm
Trisodium citrate 9gm
D.W. to 250ml
 2- Take 10ml from solution & titrate with 0.2 N NaOH solution. Using phenol red as an indicator the
end point is changing from yellow to pink .This is the End Point at zero time is represented by X
which is the volume of NaOH equivalent to aspirin before hydrolysis .
 3-Label 3 flasks with the experimental temp. 40,55,70 c˚& place about 80 ml of mixture in each.
 4-Note the time & place the flask for the elevated temperature in water bath provided.
 5-Take 10ml sample from each flask every 10 min. for one hour titrate the sample with 0.2 N NaOH
solution.
 6-Find the end point of each temperature at the time interval mentioned & represent item
Y1,Y2,Y3,Y4 ml of 0.2 N NaOH.
Assistant Lecturer Ahmad A.Y
15
Calculation
 1- The initial titration figure of Xml 0.2 N NaOH will represent 100% potency & when aspirin is
completely hydrolyzed to S.A.& acetic acid it required 2X ml 0.2 N NaOH .
 Thus the amount of aspirin remaining after partial hydrolysis would be equivalent
 ( 2X-Y) ml 0.2 N NaOH where Y is the titration figure for partially hydrolyzed sample .
 Thus percent potency is given by :-
Potency % =C%= {( 2X-Y)/ X} ˟ 100 …………Percent of remaining aspirin
 2-Take log C% & plotted against time (min) for each temperature.
 3-Find the rate constant K for each temperature from the slope of the line .
K= - Slope * 2.303 ……. ( log C2=log C1 – kt/2.303 ) use this equation to find K
 4-Take log K& plot against reciprocal time ( 1/T) ( Arrhenius plot ) to find K at 25 c˚
( log K= log A – Ea/2.303 *RT )
t ½ = 0.693/ k and t 90% = 10% * C / K
Assistant Lecturer Ahmad A.Y
16
Table 1
temp. Time ml NaOH c% logc%
Table 2
Temp.(c˚) T 1/T K logK
Assistant Lecturer Ahmad A.Y
Tabulate the result as follows :
17Assistant Lecturer Ahmad A.Y

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Kinetics 4 physical pharmacy lab

  • 1. Physical Pharmacy Lab - 4 - Kinetics Assistant Lecturer Ahmad A.Yosef 2018/2019 1Assistant Lecturer Ahmad A.Y
  • 2. 2 This lab is used to demonstrate the way at which the break down of the product occurs at elevated temperature. which is used to forecast the rate at which the activity deteriorates at temperature of storage & thus to estimate the shelf life of the product ( Expire Date ) . Kinetic Assistant Lecturer Ahmad A.Y
  • 3. 3 *Kinetics:- is the studying of reaction rate & factors affecting it. *Reaction rate:- is the velocity or the speed at which the reaction proceed ,it is given by ± dc/dt ,this expression gives + the increase or – the decrease of concentration dC within a given time interval dt. *Reaction order:- is the number of atoms or molecules whose concentration determine the reaction rate . the reaction order shows the way of how the concentration Of reactant affecting the reaction rate DEFINITIONS Assistant Lecturer Ahmad A.Y
  • 4. 4 Factors that may affecting reaction rate: 1- concentartion of reactant 2- temperature 3-catalysts 4-presence of solvents 5-light 6-pH Assistant Lecturer Ahmad A.Y
  • 5. 5 A-Zero order reaction:- the rate of reaction is independent on reactant conc. So , -dc/dt=k˳ B-First order reaction:- A→B+C So - dc/dt=k[A] C-Second order reaction:- A+B→C+D So -dc/dt=k[A][B] D-Third order reaction:- 2A+B→C+2D So, -dc/dt=k[A]²[B] Orders of reaction: Assistant Lecturer Ahmad A.Y
  • 6. 6 *half life t 1/2% :- is the time required for the drug to decompose to one half its original concentration . *shelf life t 90%:- is the time required for the drug to lose10% of it's original concentration .Or it’s the time required for the drug to degrade to 90% of it's original concentration. Assistant Lecturer Ahmad A.Y
  • 8. 8 B-First order reaction :-  Assistant Lecturer Ahmad A.Y
  • 9. 9 * To calculate t 50% Log 0.5c˳ = log c˳ - kt ½ / 2.303 kt ½ /2.303 =logc˳ - log0.5c˳ kt ½ / 2.303= log c˳/0.5c˳ kt ½ /2.303=log2 t 1/2= 0.693/ k *To calculate t 90% Log 0.9c˳ = logc˳-kt /2.303 K t/2.303 =log c˳/0.9c˳ t 90% = 0.10% /k Assistant Lecturer Ahmad A.Y
  • 10. 10 Both t1/2 & t90% are concentration Independent , thus for t1/2 it takes the same amount of time to reduce the concentration of drug from 100mM to 50 mM as it does from 50 mM to 25 mM. Assistant Lecturer Ahmad A.Y
  • 11. 11 Temperature   lnK = lnA – Ea/RT → 2.303 log K = 2.303 log A – Ea/RT Log K = log A -Ea / 2.303 RT Assistant Lecturer Ahmad A.Y
  • 12. 12 The plot known as Arrhenius plot for predicting stability at room temperature. Note:-Arrhenius found that speed of many reactions increase about 2 or 3 time with each 10c˚rise in temperature . So we can apply Arrhenius equation to find the reaction rate at temperature of storage. Assistant Lecturer Ahmad A.Y
  • 13. 13 Aim of experiment:- Studying the effect of temperature on the hydrolysis of aspirin (1st order kinetic) in order to use it as guide to estimate t ½ and t 90% Materials & equipment:- Aspirin, Trisodium citrate, NaOH Phenol red indicator ,0.2 N NaOH solution Conical flask(250ml)&conical flask(150,50 cc),pipette& burette three water baths. Assistant Lecturer Ahmad A.Y
  • 14. 14 Procedure  1- Prepare the following mixture in 250ml conical flask : Aspirin 4.5 gm Trisodium citrate 9gm D.W. to 250ml  2- Take 10ml from solution & titrate with 0.2 N NaOH solution. Using phenol red as an indicator the end point is changing from yellow to pink .This is the End Point at zero time is represented by X which is the volume of NaOH equivalent to aspirin before hydrolysis .  3-Label 3 flasks with the experimental temp. 40,55,70 c˚& place about 80 ml of mixture in each.  4-Note the time & place the flask for the elevated temperature in water bath provided.  5-Take 10ml sample from each flask every 10 min. for one hour titrate the sample with 0.2 N NaOH solution.  6-Find the end point of each temperature at the time interval mentioned & represent item Y1,Y2,Y3,Y4 ml of 0.2 N NaOH. Assistant Lecturer Ahmad A.Y
  • 15. 15 Calculation  1- The initial titration figure of Xml 0.2 N NaOH will represent 100% potency & when aspirin is completely hydrolyzed to S.A.& acetic acid it required 2X ml 0.2 N NaOH .  Thus the amount of aspirin remaining after partial hydrolysis would be equivalent  ( 2X-Y) ml 0.2 N NaOH where Y is the titration figure for partially hydrolyzed sample .  Thus percent potency is given by :- Potency % =C%= {( 2X-Y)/ X} ˟ 100 …………Percent of remaining aspirin  2-Take log C% & plotted against time (min) for each temperature.  3-Find the rate constant K for each temperature from the slope of the line . K= - Slope * 2.303 ……. ( log C2=log C1 – kt/2.303 ) use this equation to find K  4-Take log K& plot against reciprocal time ( 1/T) ( Arrhenius plot ) to find K at 25 c˚ ( log K= log A – Ea/2.303 *RT ) t ½ = 0.693/ k and t 90% = 10% * C / K Assistant Lecturer Ahmad A.Y
  • 16. 16 Table 1 temp. Time ml NaOH c% logc% Table 2 Temp.(c˚) T 1/T K logK Assistant Lecturer Ahmad A.Y Tabulate the result as follows :