TEMPERATURE
EFFECTS
Why need to know?
TR: Reference temperature
and pressure:
It is usually taken as the
standard temperature and
pressure of the enthalpy of
formation.
Temperature effects
Real reactions may generate or absorb large amounts of heataffecting T of reaction mixture
Affects rate
rate of heat addition/removal to maintain desired reaction
temperature ?
Reaction Temperature-what should it be?
Advantageous to operate exothermic reactors nonisothermally
Higher temperatures lead to higher reaction rates and smaller
reactors
If temperature too high equilibrium can limit conversion
High temperatures can lead to hot spots and reactor failure
Reference state: 25oC & 1 atm
Data available in reference texts
HR/
RAPID REVIEW
Heat capacity:
Energy/mole-K
Enthalpy of i at T
Enthalpy of formation at TR=
Enthalpy change (Tio T) for no phase change):
*
Assuming mean specific heat for components of the reaction
mixture
Heats of Reaction
NONISOTHERMAL REACTOR:
RATIONALE
=d+c-b-a
Analysis of Nonisothermal
Reactors
The energy balance is an accounting
of rate of:
heat flow into the reactor with
reactants
heat flow out of the reactor with
products
heat generated/absorbed by reaction
heat added/removed from reactor
work done by stirrers and friction
ENERGY BALANCE
Q
Inflow stream:
Control
volume of
reactor
Ws
Outflow stream:
Fi, Ti, Ei, CPi,Pi, Hi
Inflow
Outflow
Expanding
Q.2
The exothermic elementary liquid-phase reaction
A +B
-C
-rA = kCACB
is carried out in a batch reactor with a cooling coil to keep the
reactor isothermal at 27C. The reactor is initially charged with
equal concentrations of A and B at 2.0 mol/L and no C
1. How long does it take to reach 95%
conversion?
2. What is the total amount of heat (kcal) that must be removed
by the cooling coil when this conversion is reached?
3. What is the maximum rate at which heat must be removed by
the cooling coil (kcal/min) and at what time does this maximum
occur?
4. What is the adiabatic temperature rise for this reactor and what
is its significance?
Rate constant,
k =0.01725 L/mol-min, at 270C
Heat of reaction,
H R =-10 k cal/mol A, at 270C
Partial molar heat capacities:
CPA =CPB =20 cal/mol-K, CPC =40 cal/mol-K
Reactor volume:
VR =1200 L
Solution to Q.2
1. Assuming
constant density,
-rA =-[dCA/dt]
= kCACB = kCA2
1/0.01725)x(1/0.05x2.0-1/2.0)=551 min
T= HR(NA NA0)/VR CP
CPdT= HRdNA
At steady state
negligible shaft work,
ADIABATIC OPERATION:
=0
Hence
ADIABATICOPERATION: T vs. XA
Assumes negligible and
Q=0 exothermic reaction
Increasing slope
Foradiabatic operation2
Q1
What temperature must the reactor be operated at to
achieve
80% conversion in a CSTR?
Q2.
What is the heat duty of the heat exchanger inside the
reactor?
What is the heat duty of the heat exchanger placed
outside the reactor if reactor effluent must be at 250C
before storage
Approximate the heat capacity of the reaction mixture
Graphical
640
620
600
580
EB
560
540
520
500
MB
480
0
0.2
0.4
0.6
XA
0.8
1.2
Solution
Cooling coils
Jackets
Material balance unchanged, Neglecting
volume of coils
EB: Neglecting Ws
for high flow rate of coolant/heating fluid
inlet temperature = outlet temperature
simplifying yields
T/T0
X1
T1
T1/T0
X2
T2
T2/T0
X3
T3
T3/T0
-rA
[FA0/rA]
The inlet temperature and pressure are the same for both cases at
1035 K and 162 kPa, respectively
Solution:
Step1: XA=0
Step2:At
XA=0, T = T0 = 1400K;
TR=298K
Hr = iHi0 =cHC0+bHB0-aHA0=-1x74.81+1x[-61.09]-1x216.67
=88.77 kJ/mole
me: CPA=13.39;
CP cCpC + bCpB-aCpA
J/mole-K kJ/mole-K
[2-1]/1=1;
CA=CA0 [1-XA]/(1+XA)