Modern Steel Making

Prof. Dr. Mohamed Ahmed Taha

Lecture no.06
 REACTION RATES
What does rate mean ?
Can you think of an everyday measurement of rate ?
How about a car speed in miles per hour!
How about water flow in gallons per minute!
How about an audience entering a stadium in people
per hour!
What do all these measures have in common?

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REACTION RATES
(contd)
Each one contains a time unit and the word
per.Per means divide! How then is the rate
value set up mathematically?
In each case an amount unit (miles, gallons or
people) is divided by a time unit (hours, minutes
or possibly seconds).
Generally then rates are ratios (divisions) with an
amount divided by time.
Rate = amount / time

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REACTION RATES
(contd)
In chemistry, the amount unit may vary but is
often in moles, moles per liter (molarity), grams or
even liters.
Rates of chemical reactions then, are most often
measured as moles per second, molarity per
second.
Rates of reaction can be measured in terms of
reactants consumed ( negative rates) or products
produced (positive rates).

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REACTION RATES
(contd)
The progress of reactions, as reactants are
converted to products are often represented by a
graph.
When interpreting the graph it is important to
recognize whether the amount of products or
reactants is being measured !
If the reactants are being measured the direction
of the reaction and the sign of the rate will be
different than if the products are measured.
Study the following graphs and see if you can
determine the direction of the reaction and the
appropriate rates.

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 REACTION RATES
A B + C

M GRAPH 1 M GRAPH 2
O O
L L
E E FORWARD
RXN RATE?
RXN
S S FORWARD
RATE = CONSTANT
OR REVERSE?
RXN
RATE
RATE?
=0

A A

TIME TIME

M FORWARD
RXN RATE?
RXN M
RXN RATE ?
O FORWARD
RATE = OR
VARIABLE
REVERSE? O REVERSE RXN
FORWARD OR
L L RATE = VARIABLE
REVERSE RXN?
E E
S S

A A
GRAPH 3 GRAPH 4
TIME TIME 6
SLOPE OF A TANGENT LINE TO AN AMOUNT VS. TIME GRAPH = RATE
 FACTORS THAT EFFECT REACTION RATES

FIVE FACTORS CAN CHANGE THE RATE OF REACTION. CAN

YOU NAME THEM?
THEY ARE :
(1) CONCENTRATION OF REACTANTS (REMEMBER THAT
CONCENTRATION IN GASES IS DIRECTLY RELATED TO
PRESSURE, PV =nRT)
(2) TEMPERATURE
(3) SURFACE AREA OF THE REACTANTS
(4) CATALYSTS
(5) THE NATURE OF THE REACTANTS
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Reformer
Reformer
Natural gas and steam ratio fed to reformer is kept (2.44) to avoid
the formation of free carbon.
Reformed gas produced to reduction circuit= 125000 NCMH
The mixture is introduced to the reformer tubes which are packed
with nickel catalyst.
The reforming reaction:

The reformed gas produced analysis:

Catalytic tubes
Catalyst data
Reformer

Catalyst Poisoning:
The reduction in catalyst activity during reaction called catalyst poisoning, which occurs due to
some undesired reactions:

Those three reactions form free carbon, which is dangerous to the catalyst, as it may block the
catalyst holes blocking the pass of the gasses, and it also some times dissolve the catalyst.
There is another important source for catalyst poisoning, which is sulphure content in N.G which
is removed in desulphurization unit, just before mixing point.
HOW CONCENTRATION EFFECTS REACTION RATES (THE
RATE EQUATON)

THEREFORE OUR EQUATION MAY BE WRITTEN AS:

RATE = CONSTANT x CONCENTRATIN RAISED TO SOME
POWER OR
RATE = k x [A]n
k = A CONSTANT CALLED THE SPECIFIC RATE CONSTANT
(IT IS CONSTANT FOR A SPECIFIC REACTION AT A SPECIFIC
TEMPERATURE)
[A] = THE CONCENTRATION OF REACTANT A IN MOLES
PER LITER (BRACKETS MEAN IN MOLES PER LITER)
n = THE POWER TO WHICH CONCENTRATION MUST BE
RAISED (ALSO CALLED REACTION ORDER)

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 HOW CONCENTRATION EFFECTS REACTION RATES
(INITIAL RATES)
USING THE METHOD OF INITIAL RATES REQUIRES THAT A REACTION BE
RUN AT SERIES OF DIFFERENT STARTING CONCENTRATIONS AND THE
RATE BE DETERMINED FOR EACH.
GIVEN THE FOLLOWING DATA FOR THE REACTION
A B+ C
(TABLE 1)
EXPT [A] RATE (M/SEC)
1 1 x 10 -3 4 x 10 -1
2 2 x 10 -3 8 x 10 -1
3 4 x 10 -3 16 x 10 -1
AS CONCENTRATION OF A DOUBLES, RATE DOUBLES. THE REACTION IS
FIRST ORDER IN REACTANT A
RATE = k[A]1 OR RATE = k[A]

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 HOW CONCENTRATION EFFECTS REACTION RATES
(INITIAL RATES)
FOR THE REACTION: A + B C + D
(TABLE 2)
[A] [B]
1 1 x 10 -3 1 x 10 3 4 x 10 -1
2 2 x 10 -3 1 x 10 -3 8 x 10 -1
3 1 x 10 -3 2 x 10 -3 16 x 10 1
USING EXPT 1 AND 2, [A] DOUBLES AND [B] IS CONSTANT. THE
DOUBLING OF THE RATE IS THEREFORE CAUSED BY REACTANT A
AND THE ORDER WITH RESPECT TO A IS FIRST.
USING EXPT 1 AND 3, [A] IS CONSTANT AND [B] IS DOUBLED. THE
FOUR TIMES RATE INCREASE IS THEREFORE CAUSED BY REACTANT
B AND THE ORDER WITH RESPECT TO B IS SECOND.
RATE = k[A]1[B]2 OR RATE = k[A][B]2
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 Equilibrium between the phases:
The phases in steelmaking are hot metal, molten slag and gas. Hot metal is a
multi-component solution in which impurities like carbon, silicon, manganese,
phosphorus and sulphur are dissolved in very low amount (total concentration of
all the impurities is approximately 5% to 6%) in iron. Slag is a solution of
predominantly oxides with small amounts of sulphides, phosphides, silicates etc.
Composition of the solutions in steelmaking is conveniently expressed either as
weight% (Wt%) or mole fraction(N). The mole fraction of the I th component in a
solution of n components is
 Diffusion : Ficks Diffusion Laws
The quantity of diffusing substance which passes per unit time through unit area of a plane
perpendicular to the direction of diffusion, known as the flux J, is proportional to the
concentration gradient of the diffusing substance

The coefficient D is the diffusivity of the substance in the medium; C is the concentration of the
substance per unit volume and x the distance in the direction of diffusion. The second law is for
the non steady state diffusion.The rate of accumulation of diffusing substance in a given volume
element is the difference between the inward and outward flux. In other words, what goes in and
does not come out, stays there. The rate of concentration change -dC/dt resulting from flux over a
distance dx is