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dC A rA = = kC A dt
t dC A = k dt CA C 0 CA
A0
CA ln = kt CA
0
NA NA
0
NA
NA CA = = NA V
0
1 xA = C A (1 x A ) V
0
0
CA = CA CA x A dC A = 0 C A dx A
0
dC A = C A dx A
0
dt
= k (C A C A x A )
0 0
dx A = k(1 x A ) dt
xA t dx A = k dt 0 1 xA 0
ln(1 x A ) = kt
What if
dC A .6 0 .4 = kC0 A CB dt
Then
dx A rA = C A = k(C A C A x A )(CB C A x A ) dt
0 0 0 0 0
Let M =
CB CA
dx A rA = C A = kC2 A (1 x A )(M x A ) dt
0 0
xA
t dx A = CA k dt 0 (1 x A )(M x A ) 0
0
dC A = kCn A dt
Integrating for n 1
n 1n C1 C )t A A = k (n 1
0
k L = k
Defining the half-life as the time needed for the reduction of concentration of reactant for one-half of the original value then we get
2n1 1 1n CA t = k(n 1)
1 2 0
Differential method of analysis of data Guess the rate equation Find (1/V)(dN/dt) Plot of the data
Rate equation is satisfied by the data.
Good fit
Unfit
2. Plot concentration vs. time from experimental data 3. Draw a smooth curve through the data. 4. Determine the slope at each concentration.
If we obtain straight line through the origin, our mechanism is consistent to the data. If not hypothesize another one.
Vx
A=
A=
Vx
No conversion
Complete conversion
NA = NA (1 x A )
0
Therefore
NA NA (1 x A ) (1 x A ) CA = = = CA V V0 (1 + A x A ) (1 + A x A )
0 0
Thus
CA 1 xA = CA 1 + A x A
0
or
CA 1 CA xA = ACA 1+ CA
0 0
or
dx A rA = (1 + A x A ) dt
0
CA
If A = 0
dx A rA = C A dt
0
Constant-volume
Integral method of analysis The analysis requires again the integration of the rate expression to be tested. For T, P = constant
C A dx A 1 dNA rA = = V dt 1 + A x A dt
0
CA
xA
0
t dx A = dt = t 0 (1 + A x A )( rA ) 0
Differential method of analysis The procedure is the same as for constantvolume batch reactor analysis except that we must replace
dC A dC A d ln V by + CA dt dt dt dx A or 1 + A x A dt
0
CA
CA
xA
0
t dx A = dt 0 (1 + A x A )( rA ) 0
CA
xA
0
CA CA dx A V = ln(1 + A x A ) = ln = kt A A V0 0 (1 + A x A )
0 0
rA =
dx A (1 + A x A ) dt
0
CA
dx A kC A (1 x A ) rA = = 1 + A x A dt 1+ A x A CA
0 0
xA
V dx A = ln(1 x A ) = ln1 = kt 0 1 xA A V0
The rate is
rA = kC2 A
C 1 A CA xA = C 1+ A A CA
0 0
rA =
dx A (1 + A x A ) dt
0
CA
dx A rA = = kC2 A 1 + A x A dt
0
CA
1 xA 1+ A x A
xA
1+ A xA (1 + A )x A dx A = + A ln(1 x A ) = kC A t 2 1 xA 0 (1 x A )
0
nth-order reactions
1 xA rA = kC = kC 1+ A x A
n A n A0 n
From
CA
xA
0
t dx A = dt = t 0 (1 + A x A )( rA ) 0
We obtain
xA
(1 + A x A )n1 n1 dx A = CA kt n (1 x A ) 0
0