Cinetica Teoria - FANTASTICO

FScN 8334
Topic 2
Reaction Order
Determination
and reaction kinetics
Topic 2 Or der Det er mi n a t i on Page # 2
I. General definitions
A. general equation for equilibrium
k
aA bB cC dD
k
K
C D
A B
k
k
f
b
eq
c d
a b
f
b
+ +
[ ] [ ]
[ ] [ ]
]
]
]

[X] = concentration of each species
a,b,c etc = stoichiometry # of species to give mass balance
k
f
= forward rate constant (units depend on stoichiometry)
k
b
= backward rate constant
K
eq
= equilibrium constant
B. Relationship to thermodynamics
G H T S RT K
eq
ln
C. molecularity vs stoichiometry
molecularity - actual # of reacting species
stoichiometry - # to mass balance equation
molecularity stoichiometry
(1) A --------> C 1 A --->C
(2) A +A-->A + A*---->A + C 2 A ---->C
D. Water
In general neglect water as reactant as concentration is 55 M/L
and does not change with reaction extent.
? of low moisture systems
? of pH - if H
+
or OH
-
catalyzed - especially as water content
changes
II. Reaction order
A. Gener alized r at e equat ion
t
[ ] [ ]

dA
dt
k A B
n n
a b
rate of gain or loss per unit time
= amount / time
k = rate constant
[A] = concentration
[B] = concentration
n = order with repect to A or B
x
B. Order definitions
overall order = sum of exponents = a+b = n
dA
dt
k A B
a b
[ ] [ ]
specific order - may not be the stoichiometric parameters,
rather it is the curve fitting parameters
GEORGE BOX :
ALL MODELS ARE WRONG BUT SOME ARE USEFUL
for A order = a
for B order b
for A -> C overall order = 1
for A + A -> A + C order = 2
order can be fractional - complex reaction
order can be zero -
- change in A negligible over time eg drug in
suspension
- not true stoichiometry
pseudo order - mechanism unknown - curve fitting
C. Units convention for rate constant
mass balance
A B C + >
2 3
moles = 0
dA
dt
k A B
dB
dt
k A B k k
dC
dt
k A B k k
dA
dt
dB
dt
dC
dt
A
B b A
C C A

[ ][ ]

[ ][ ]

[ ][ ]

+
|
.
`
,
+
|
.
`
,
+
2
2
2
2
3
0
thus always look at how the rate constant was measured
D. Reaction Rate for simple two component equilibrium reaction
1. reaction (example: mutarotation of reducing sugars in
solution)
k
A B
k
K
B
A
k
k
f
b
eq
f
b
[ ]
[ ]
]
]
]

2. boundary conditions for equilibrium reactions
at time = 0 A = A
o
at time = t A=A
o
- x B = x
at time = t
eq
B = X
e
A=A
o
- X
e
3. solution
+ [ ] [ ]

[ ]
[ ]

[ ]
[ ]
[ ]

[ ][ ]

[ ]
dB
dt
dA
dt
k A k B
k A x k x
K
k
k
x
A x
k k
A x
x
dx
dt
k A x k x k A x
k
x
A x x
k
x
A x xx
f b
f o b
eq
f
b
e
o e
b f
o e
e
f o b f o
f
e
o e
f
e
o e e

[ ][ ]

[ ]
k
x
A x x
k
x
A x x
f
e
o e
f
e
o e
ln ln
A A
A A
B
B B
k
B
A t k k t
o e
t e
e
e
f
e
o f b
]
]
]

]
]
]
+
[ ]
thus plot either the A or B function vs time .
Need to know A or B as function of time and A
o
and either A
e
or B
e
E. Complex reactions
A--->B---->C
at time = t =0 A
o
=A
at time = t A
o
= A + B + C (mass balance)
dA
dt
k A A A e
dB
dt
k A k B
B A A C A e C
dC
dt
k B k A e k C
dC
dt
k C k A e
A o
k t
A B
o o
k t
B B o
k t
B
B B o
k t
A
A
A
A

[ ]

[ ]
+
[ ]
1
1
1
Topic 2 Or der Det er mi n a t i on Page # 1 0
first order differential equation general solution
dy
dx
P is function such that P' (x) = p(x)
+
( )

p x y q x
P x p x
e
y q dx c
x
P x
x x x
( ) ( )
( )
( )
( )
( ) ( ) ( )

Th u s :
B
k A
k k
e e
C k A
k
e
k k
e e
A o
B A
k t k t
B o
B
k t
B A
k t k t
A B
B A B

[ ]

( )

( )
]
]
]

1
1
1
Stepwise solution for magnitudes of rate constants
Plot A vs time ---> k
A
from slope
for B and C
need to solve for constants by curve fitting techniques
no simple plots - use non-linear regression techniques
eg Excell Solver Function
JMP
Sigma Plot Curve Fitting Function
solve for k
B
first as know k
A
from ln A vs time plot
use Levenburg- Marquat or Rungga Katta techniques
then do the same for same for C as a function of time
III. Order determination

[ ]
dA
dt
k A
A
n
A. Method of differentiation
1. plot concentration vs time. and draw smooth curve (fig 2-1)
2. slope is dA/dt.
determine slope at various points in time by:
a. drawing tangent to curve
b. taking A for each t (need lots of data points)
3. plot ln dA/dt vs ln A as in Figure 2-2
ln ln ln
dA
dt
k n A
A
[ ]
+
[ ]
slope = n the order
rate constant from algebraic substitution
Figur e 2-1 Figur e 2-2
4. Class example
` a. slope determinations
order close to 1
rate constant 0.06 units (time^ -0.68)
5. On-line computer instrument analyzers - depends on time
differential used and reaction rate.
B. Method of integration
1. Order = 0 pseudo zero order
a. general solution
[ ]

[ ]

dA
dt
k A k
dA k dt
A A k t
A A k t
z
z
t
A
A
z
o z
0
0
0
0
plot A vs time ---> straight line
or plot A
o
-A vs time --> straight line
slope = rate constant = k
z
k
A A
t t
z

2 1
2 1
units = amount per time (eg mg/L hr)
b. data for amount vs time for zero order plot
c. draw line on graph and calculate slope (next page)
d. results
class value k
avg
= (95% CL) = t/n
my value k
z
=
e. linear regression generated results
k
z
= 0.7718 units/time 0.128

(95% CL)
k
upper
= 0.90 k
lower
= 0.644 r
2
= 0.954
Figure 2-3 Example from nonenzymatic browning
2. first order
a. derivation of equations

]
]
]

]
]
]

]
]
]

dA
dt
k A
dA
A
k dt
A
A
k t
A
A
k t
A A e
A
A
k
t
A A
f
A
A
f
t
f
f
k t
f
k
t
f
f
0
0
0
0
0
0
0
2 303
2 303
10
ln
ln
log
.
.

[A]
time
log
slope * 2.3=k
b. rate constant units = time
-1
k
f
= slope of ln [A] vs t plot
= slope of ln [A/A
o
] vs t plot
k
f
= 2.3 * slope on semi-log plot of [A] vs time
or of semi-log plot of [A/A
o
] vs time
k
A
A
t
f
2 303
10
.
log
[ ]
[ ]
c. class t est dat a

d. results of calculations
instructor k
f
=
class k
f
= (95%CL) = t/n
linear regression slope = 0.00634 time
-1
(r
2
= 0.989)
thus k
f
=2.3 * slope = 0.0146 0.0012 (95%CL)
k
upper
=0.0158 k
lower
=0.0134
Figure 2-4 Example of first order Ascorbic acid loss
e. first order production of quantity B starting with quantity A
o
(1) mathematical derivation note assumes all A -> B
A B
at t A A B
at t A B B
at t t B A A A A B
A A e
A B A e
B A e or B B e
kt
kt
kt kt
0 0
0
1 1
0
0 0
0
0 0
0
( ) ( )
non linear solution
solve for k
here B
eq
is value when all A-->B
can assume at large time B= B
e
= A
o
Note: usually only can measure A or B not both
B
t ime
B
eq
Not e:
ln ln ln( ) B B e
kt
+
1
b. algebraic plot solution
algebraic solution
dB
dt
kA A A B
dB
A
dB
A B
kdt
A B
A B
kt or
B B
B B
kt
if B then B A
A
A B
kt
o
B
B
o
B
B
o
t
o
o o
+
[ ]
[ ]

[ ]
[ ]

[ ]
[ ]

ln ln
ln
0 0
0
0
0
0
0
0
can plot ln(function) vs time to get slope = k
need good estimate of B
eq
when A
o
value not known
3. Other orders when n not equal to 1
a. derivation of rate equation (one reactant)
dA
dt
k A
dA
A
k dt
A A
n k t
A
n k
n
n
n
A
A
n
t
n
n
f
n
f
[ ]

]
]
]

]
]
]
[ ]
]
]
]
[ ]

0
0
1
0
1
1
1 1
1
1
1
for n 1
plot vs t
slope =
positive or negative slope depending on loss vs gain
can also plot Y = A
(1-n)
*(1/1-n) vs time gives straight line with slope of k
basis of Macintosh computer program ( same plot for n = 2)
b. class example for second order
A + A ----> B
n=2 therefore 1-n = -1
plot Y= [A]
-1
vs time
slope = k
k = (concentration time)
-1
eg mM
-1
L
-1
c second order plot
second order n=2 r
2
= 0.949
slope = k = 0.000313 0.0001
k
upper
= 0.000413

k
lower
= 0.000213
d. Two reactants (each 1st order)
A + B ----> C

[ ][ ]

[ ]
]
]
]

]
]
]

]
]
]
+
[ ]
]
]
]

[ ]
dA
dt
k A B
dC
dt
dx
dt
A A x
B B x
C x
A x
B x
A
B
A
B
A B kt
A
A
B
B
A B kt
o
o
[ ] [ ]
[ ] [ ]
ln ln ln
ln
0
0
0
0
0 0
0
0
0 0
(1) if can measure A and B independently then
plot ln [A/B] vs time
slope = [A
o
-B
o
] k
(2) if know A
o
and B
o
and can measure C then
plot ln[(A
o
-C)/(B
o
-C)] vs time.
same slope = [A
o
-B
o
] k
(3) if all three measurable can make both plots and
compare k values - allows for ? of accuracy of
measurement
(4) can also assume initial rate holds
measure loss of A k
A
= k [B
o
]
measure loss of B k
B
= k[ A
o
]
find k separately either way
compare to plot for both simultaneously
(5) same as (4) but also measure C
if smaller suggests that C---> D
(6) examples ascorbic acid + oxygen in package
amino acid + reducing sugar (NEB)
(7) error based on error of measurement of concentrations
C. Method of half lives
1. first order n=1
ln
ln ln . .
.
A
A
k t
A
A
k t
k
t
t
o
f
o
f
f
]
]
]

]
]
]
]
[ ]

1
2
0 5 0 693
0 693
0
1
2
1
2
1
2
half life in time units
from above example
A= 1/2 A
o
when t = 50 time units
thus k
f
= 0.693/50 = 0.0.01386 time
-1
should run experiment through 2 - 3 half lives
Ascorbic acid half life data
system half-life days @ F
canned OJ 300 100
frozen veges 240 10
IMF no oxygen 70 82
IMF in air 12 82
IMF in air 5 100
dry tomato 180 100
dry potato 24 100
2. life for any fractional decrease
where f = decimal fraction (A/Ao) and n=1
ln
ln ln
ln
A
A
k t
fA
A
f k t
k
f
t
t
o
f
o
f f
f
f
f
]
]
]

]
]
]

[ ]

0
fraction life in time units
(a) eg for decrease by 1 log cycle ie 1/10 of original
as in microbial death where f=0.1
ln
ln
.
ln .
ln . .
.
log . .
.
.
.
A
A
k t
A
A
k t
k
D D D D
D
k
t D
o
f
o
f
f
f
]
]
]

]
]
]
[ ]
0 1
0 1
0 1 2 3026
2 3
0 1 2 3
2 3
0
0 1
0 1
value in time for 1 log cycle decrease
(b) drug stability time to 10% loss f=0.9
t
k k
0 9
0 9 0 11
.
ln . .

3. half life for second order where n=2

[ ]

[ ]
[ ]

dA
dt
k A k A
dA
A
kdt
A A A
kt
t
kA
A
A
A
t
o o o
o
2 2
2
0 5
0
1
2
1
2
2
2 1 1
1
0
0
1
2
.
4. half life for any order n except n=1
t
k n A
n
o
n
1
2
1
1
1
1
2 1
[ ]

D. Other methods for order determination
1. Initial rate for complex reactions
- assume pseudo first order with respect to A
- assume all others are constant (B etc.) ie small change
eg. A +B ----> C
dA
dt
k A B
dA
dt
k A
k k B
B
B

[ ][ ]

[ ]
[ ]
assume B>> A
log plot of [A] vs time ---> k
B
k
B
[B
o
] = k
2. Powell Plot method (n 1)
1 1
1
1
1 1 1
1
1
1
1
1 1
1
1
1
1 1
A A
n kt
A A n kt
A
A
n A kt zt
z n A k
A
A
A
A
n
o
n
n
o
n
o
n
o
n
o
n
o
n
o
]
]
]

]
]
]

[ ]

[ ]
]
]
]
+ +

]
]
]

]
]
]

( )
( )
nn
n
x p
o
o
zt
also y p y
p y
n
A
A
zt
A
A n
z
n
t

+ +
[ ]
]
]
]

[ ]
]
]
]

[ ]
+
[ ]
1
1 1 1
2
1
1
1
1
1
1
2
ln
ln
!
( ) ln ln
ln ln ln
for small change 3rd term small thus:
do linear regression of ln A/A
o
vs ln time
slope = 1/1-n
get k from intercept value (1/1-n) ln z
original paper has A/Ao vs log t lines for different n values
choose the one that is the closest
3. Wilkinson plots ( Chem. & Ind. 9/2/61 pg. 1395)
1 1
1
1
1 1
1
1
1
1
1
1 1
1
1
1
A A
n kt
A A n kt
A
A
n A kt
set f
A
A
A
A
f
A
A
f
n
o
n
n
o
n
o
n
o
n
c
o
o
c
o
n
c
]
]
]

]
]
]
[ ]
[ ]
]
]
]
+

]
]
]

( )
(fraction consumed)
f =1 when A = A
o
[[ ]
+

[ ]
+

[ ]
+

[ ]

1
1
2 3
1
2
1
1 1
0
1
1 1
1
2
1 2
3
1 1 1
1
2
1 1
n
o
n
c
x
c
n
c c
c
n
n A t
for n f zt
k
A
t
for n
y xy
x x y x x x y
f n f
n n
f
f
( )
( )
!
( )( )
!
( )
( )
series expansion
drop last term
++

+
( )
( )
( ) n f
n nf
n A t
f k t
n
f
f
f k t
f k t
n kt
f
f
t
k
n k
f
c
c
o
n
c c
c
c
c c
c
c
1
1
2
1 1
2
2
2
2
1
2
subtract 1s and divide by n -1
= A
if small (small extent) then
A (essentially zero order at start)
substitute in for one value of f
= A
A
A
A
o
n-1
o
n-1
o
n-1 o
n-1
o
n-1 o
n-1
tt
f k
nt
+
1
2 A
o
n-1
plot t/f
con
vs time where f
con
= fraction consumed =1-A/A
o
slope of line is n/2
derivation is not 1st order but paper says use anyway
at small t and f
con
t/f
con
-->
t /f
f
t est of Wilkinson plot wit h same dat a
t /f con
0

plot of all data
Note poor fit of line
from plot order = 2 * 0.21 = 0.42
plot of data after time =10
from modified plot
order = 2 * 0.55 = ~ 1.2 so closer but not a good method
E. Other important factors
1. Error of % basis for zero order
suppose 1 mg/day loss rate and:
A
1
=100 or A
2
=200
then at t = 50 A=100-kt A=200-kt
A=100-1*50=50 A=200-1*50=150
% %
%/ . %/
day
x
day
x
day day

100 50
100
50
100
200 150
200
50
100
1 0 5
thus %/day depends on initial value of A for zero order
not a problem for 1st order
2. fraction consumed - zero order
A A kt
A A
A
A
A
f
A A
A
k
A
t f
f
k
A
t
k
A A
t
f
A
A
t
t
k
A
t
f
k
A
t
o
o
o o
rem
o
o o
con
rem
o
o s
s
con
s
o s
o
s
con
o

]
]
]

amount lost
f
thus plot f vs time - - > straight line
or f vs time
if set A =100% shelf life and A = 0% then

con
con
rem
o s
1 1
1
1
tt
t
A
A
f
s o
rem
1 1
plot fraction consumed vs time -->straight line
slope = k/A
o
-A
s
= 1/t
s
fraction consumed at any condition = time/total time to 100% done
3. first order fraction consumed
ln
log( ) log( )
A
A
kt
A
A
e
f f e
f e
f e
o
o
kt
rem con
kt
con
kt
con
kt

1
1
1
plot log fraction remaining vs time as before
plot of log fraction consumed vs time not a straight line !!!
while plot of fraction remaining is ie ln A/A
o
vs time
4. Choice of best order
a. best fit with highest r
2
? of meaning of linear regression
with 6-8 points need r ~ 0.95 (r
2
= 0.9)
change order regresses something different
standard error (SE) also different units
b. # of data points
should have at least 6-8 points spread over 30-50% loss
c. degree of change
For example if:
at t =0 A=100
at t=50 A=50
then
k
z
= (100-50)/50 = 1 unit/day
k
f
=0.693/50=0.01386 (units time
-1
)
time zero first
0 100 100
10 90 87
20 80 75.8
30 70 65.98
40 60 57.4
50 50 50
thus makes little difference for first 50% loss because of
analytical errors
d. maximum analytical error (From Benson) error propagation
x F p q
F
p
F
q
F
p
F
q
k
C C
t
x p q pq
k
C C
o
t
C C
o
o
|
.
`
,
+
|
.
`
,
+
|
.
`
,
|
.
`
,
( )
+
( , ,....)
( )
( )
2
2
2
2
2
2
2
2
2
2
2
2
2
2
for zero order
C = C - kt k =
C - C
t
o
o
22 2 2
+
C C
o
if at time = 1 C
o
= 1 and C = 0.9 with relative error (analytical precision) of 1% in
measurement of C and 1% error in measurement of time then:

( )
( . ) . .
.
.
.
.
. .
C C C C
k
k
k
o o
x
k
x
k
k
+ + ( )
]
]
]
+
[ ]

2 2 2 2 2 4
2
2
4
2
2
2
0 01 0 009 1 81 10
1 81 10
0 1
0 01
1
0 0182
0 135 0 135
if at t= 10 C = 0.5 then

( )
( . ) . .
.
.
.
.
. .
C C C C
k
k
k
o o
x
k
x
x
k
k
+ + ( )
]
]
]
+
[ ]

2 2 2 2 2 4
2
2
4
2
2
2
4
0 01 0 005 1 25 10
1 25 10
0 5
0 01
10
5 01 10
0 0024 0 0224
Thus inaccuracy depends on magnitude of C
o
-C and time as well as
inaccuracies in time and concentration measurement
% error in k at % change in reactant monitored
Analytical
precision % 1% 5% 10% 20% 30% 40% 50%
0.1 14 2.8 1.4 0.7 0.5 0.4 0.3
0.5 70 14 7 3.5 2.5 2 1.5
1 >100 28 14 7 5 4 3
2 >100 56 28 14 10 8 6
5 >100 >100 70 35 25 20 15
10 >100 >100 >100 70 50 40 30
e. should do multiple zero time values for precision
f. problem of extraction vs analytical test
IV. Statistical analysis of rate constants
A. Evaluation of variance
1. Gaussian distribution
(a) mean distribution is 2 for 95.43% confidence
is measure of variation of individuals in population
2
is the variance
Range of confidence =
x
_
t 2
S
e
=standard error = variation of sample means
(b) for a large amount of data, the 95% confidence limits are:
x
n
t 1 96 .

where
2
2
1

[ ]
x x
n
(c) coefficient of variation (CV) is:
cv
x

100
(d) variability at any %CL is:
x t
n
t t
n
T
T
t
value at degrees of freedom

and desired probability
= n
# of data points
T
2
Statistical significance says that data are adequate to reject the
null hypothesis that two systems are the same. Practicality is
based on how big a difference is important which must be
answered on other than statistical reasons.
Type I () error: hypothesis A=B when data says A B
Type II() error: hypothesis AB when data says A=B
Table shows need for high # of points to lower t value (>8)
? of time, cost, and reliability
(e) Student t Table = degrees of freedom = n-2
p=90% p=95% p=99%
1 6.31 12.7163.66
2 2.92 4.30 9.93
3 2.35 3.18 5.84
4 2.13 2.78 4.60
5 2.02 2.57 4.03
6 1.94 2.45 3.71
7 1.90 2.37 3.50
8 1.86 2.31 3.36
9 1.83 2.31 3.36
10 1.81 2.23 3.17
11 1.80 2.20 3.11
12 1.78 2.18 3.06
13 1.77 2.16 3.01
14 1.76 2.15 2.98
15 1.75 2.13 2.95
16 1.75 2.12 2.92
17 1.74 2.11 2.90
20 1.73 2.09 2.85
25 1.71 2.06 2.79
30 1.70 2.04 2.75
40 1.68 2.02 2.70
50 1.68 2.02 2.70
60 1.67 2.00 2.66
80 1.66 1.99 2.64
100 1.66 1.98 2.63
above 6-8 points, doubling the points reduces the t by about
10% so question of error allowed vs cost of doing more points
Going from 10 to 20 points decreases error by only 5%
B. Linear regression
1. definition : minimize sum of squares of y from fit of linearized
function.
ie least vertical deviation from straight line fit.
Major assumption (time is exact - ie not a variable!!!)
cannot really compare different type functions
same is true for standard error comparison
2. equations
Intercept = I =
I
y x x xy
n x x
[ ][ ]
[ ][ ]
[ ]
[ ]

2
2
2
Slope = k =
k
n xy x y
n x x
[ ]
[ ][ ]
[ ]
[ ]

2
2
True intercept = =
t +
[ ]
[ ]
[ ]
]
]
]
]

I t s
n
x
n x n x
e
1
2
2 2
2
1
2
True slope = =
t
[ ]
[ ]
k
t s
n x x
n
e
2
2
Standard error = se =
`
s
y I y k xy
n
e

[ ]
[ ]
[ ]
]
]
]
]

2
1
2
2
Coefficient of determination r
2
(r =correlation coefficient)
r
n xy x y
n x x n y y
2
2
2
1 2
2
2
1 2
2
[ ]
[ ][ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
]
]
]
]
]

3. Predicted future value and 95% confidence limits:
within data limits first term of 1 is deleted
y I kx t s
n
n x x
n x x
o e 0
0
2
2
2
1
2
1
1
t t + +

[ ]
[ ]
[ ]
]
]
]
]

( )
4. Comparison of rate constants
If hypothesis is k
1
= k
2
then they are the same if
(a) the 95% confidence limits overlap
significant difference (actually > 95%) rigorous test
k
1
k
2
<------------------------>
<--------------------->
(b) t test of significance - Two tailed
= 2(n-1)
t
k k
S S
t t
e e
table

+
>
2 1
2 1
2
95 significant if @ %
5. Dealing with the zero/zero time point in regression
force fit or error of measurement
6. Point by point method: (can use spread sheet)
treat each data point as one experiment and get k and 95%CL
from table
k
A A
t
k
A
A
t
k
k
n
t
n
z
o
f
avg
]
]
]
t
ln
0

7. Quality of the regression value
r (correlation coefficient) must be greater than at given level of significance
n=# of dat a pair s =95% =99% =99.5
3 0.997
4 0.950 0.990 0.999
5 0.878 0.934 0.959
6 0.811 0.882 0.917
7 0.754 0.833 0.875
8 0.707 0.789 0.834
9 0.666 0.750 0.798
10 0.632 0.715 0.765
11 0.602 0.685 0.735
12 0.576 0.658 0.708
13 0.553 0.634 0.684
14 0.532 0.612 0.661
15 0.514 0.592 0.641
16 0.497 0.574 0.623
17 0.482 0.558 0.606
18 0.468 0.543 0.590
19 0.456 0.529 0.575
20 0.444 0.516 0.561
21 0.433 0.503 0.549
22 0.423 0.492 0.537
27 0.381 0.445 0.487
32 0.349 0.409 0.449
37 0.325 0.381 0.418
42 0.304 0.358 0.393
47 0.288 0.338 0.372
52 0.273 0.322 0.354
62 0.250 0.295 0.325
72 0.232 0.274 0.302
82 0.217 0.256 0.283
92 0.205 0.242 0.267
from R.Fisher and Y. Yates Statistical Tables for Biological, Agricultural, and Medical Research Oliver &
Boyd Ltd., Edinburg.
Note that with a good r
2
of 0.95 you can be assured of a high quality (95%
CL) at only 4 data points. For 6 data points if the r
2
exceeds 0.66 you have
high quality (p = 0.95)
8 Other considerations
a. minimize residual sum of squares in estimate vs actual value
Y f x t e
RSS y f x t
i i i
i i
i
n
+

[ ]
( , )
( , )
1
2
where
y
i
= actual value
model = f(x
i
, t)= estimate at x
i,
t
i

residual difference = e
i
= y
i
- y
model
b. make residual plots (e
i
vs time)
homoscedastic = equal propagation
var(e
i
) = constant=
2
yi-f(x,t )
t ime
0
heteroscedastic = convergence or min/max
var(e
i
) = non-constant =
2
/w
i
yi-f(x,t )
t ime
0
conver ge
or diver ge

yi-f(x,t )
t ime
0
min or max
ie weighted by some unknown or error factor
should always make residual plot (good test of quality of
model)
c. Linear models not necessarily straight line
rule : derivative with respect to parameter is independent
of parameter, thus for
y ax bx cx
y
a
x
y
b
x
y
c
x
+ +

2 3
2 3

d. transformation of non-linear model to linear form
y ae
y a bx
y x
a b
y y
x
bx
+
+

ln ln
ln
* *
*

1
e. transformation weights w
i
where
RSS w y f x t
Transformation weight
y
y
y
y
y y
i i i
i
n
i
i
i
i
i
i
i i i

[ ]
( , )
ln
1
2
4
2
2
2
2
1
f. non-linear regression
need to estimate initial values
use iterative solution of some search procedure
minimize RSS
gives approximate confidence limits
danger of local minimum
gives different value at t = 0
9. Use of Mac Program -
a. review of steps
(1) enter data for A vs time
(2) choose possible orders
(3) calculate k and 95% CL for given temperature
note for n not = 1 y value is A
(1-n)
*(1/1-n)
(4) predict future values
(5) make plot with 95% CL for order
(6) repeat for each temperature
(7) choose temps and calculate E
A
and Q
10
(8) make Arrhenius plot
(9) calculate k for any temperature
b. init ial scr een
b. dat a input : example of class dat a
d, or der det er minat ion
e. zer o or der plot
f. fir st or der plot
g. second or der plot

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c. class t est dat a

Topic 2 Or der Det er mi n a t i on Page # 3 5

Topic 2 Or der Det er mi n a t i on Page # 3 6

value at degrees of freedom

Topic 2 Or der Det er mi n a t i on Page # 5 6

Topic 2 Or der Det er mi n a t i on Page # 5 9

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