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graphs as part of some of you laboratory reports and how to use the information

obtained from these graphs to perform the appropriate calculations.

Title

(liters)

Axis labels

(atmospheres)

(liters)

(torr-1)

(x1, y1)

(x2, y2)

Y

= mx +

The following table shows the rate constants for the rearrangement of methyl

isonitrile at various temperatures (these are the data in the table:

(a) From these data, calculate the activation energy for the reaction.

ln k = -(Ea/RT) + ln A

Must be in Kelvin units

Solve: (a) We must first convert the temperatures from degrees Celsius to

kelvins. We then take the inverse of each temperature, 1/T, and the natural log

of each rate constant, ln k. This gives us the table shown at the right:

methyl isonitrile

(x1,y1)

(x1,y1)

(Kelvin-1)

ln k = -(Ea/RT) + ln A

slope = m = -Ea/R

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The slope of the line is obtained by choosing two well-separated points, as shown, and using the coordinates of

each:

Because logarithms have no units, the numerator in this equation is dimensionless. The denominator has the

units of 1/T, namely, K1. Thus, the overall units for the slope are K. The slope equals Ea/R. We use the value

for the molar gas constant R in units of J/mol-K (Table 10.2). We thus obtain

We report the activation energy to only two significant figures because we are limited by the precision with

which we can read in the graph.

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1. The following equation is used to calculate the enthalpy of reaction by measuring the

equilibrium constant for that reaction at various temperatures.

ln Keq = H/RT + constant

In this equation Keq is a equilibrium constant specific for a given chemical reaction, H is the

enthalpy of reaction, R is a constant = 8.3145 J mol1 K1 , and T is the temperature in units of

Kelvin. This equation has the same form as the equation of a straight line (y = mx + b), where m

is the slope of this line and b is the intercept (the value of y when x = 0). A plot of ln (natural

log) Keq vs. T will give a straight line with slope = H/R .

The following experimental data was obtained for the reaction

CO(g) + H2O(g)

Keq

210

73

31

16

CO2(g) + H2(g)

T (K)

478

533

588

643

Using the above information to determine H from a plot of ln Keq (y-axis) vs. 1/T (x-axis).

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2. Chemical reactions occur at a wide range of rates. Some are very fast (chemical explosions,

neutralization reactions...). Others are very slow (rusting of iron, cooking, the aging process).

Chemical kinetics is the area of science that study the rates of chemical reactions and the factors

that control these rates.

The Arrhenius equation relates the rate constant of a chemical reaction (this constant is specific

for a given chemical reaction and it only changes with temperature changes) with the activation

energy (the minimum energy the molecules must have to react).

The Arrhenius equation is k = AeEa/RT , where k is the rate constant, A is a constant, Ea is the

activation energy, R is a constant = 8.3145 J mol1 K1 , and T is the temperature in Kelvin units.

Using natural logs on both sides of this equation we obtained,

ln k = Ea/RT + ln A

A plot of ln k (y axis) vs. 1/T (x-axis) will result in a straight line with slope = Ea/R and

intercept = ln A. Using the tabulated data below determine the Ea energy for a chemical

reaction from a plot of ln k (y axis) vs. 1/T (x-axis).

k (L mol1 s1)

0.0521

0.101

0.184

0.332

T (K)

288

298

308

318

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