The rate law

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The rate law

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dye m

er thanan or equalRate law:

d c dye

r=

=k

dt

r : rate of reaction

m ,n : order of reaction

k : proportionality constant

Calculate

dr

dc

instead of

E.g. 2[ bleach] : fading of food dye occurs twice as fast

For coloured bleach, use spectrometer to measure change in A

and Beers Law to convert A c

For colourless bleach, measure c indirectly

2. Determine rate law (whether m=0,1,2 ) graphically using kinetic trace

dr

, then perform

d c bleach

experiment to determine m

4. Use Beers Law to convert

analytical

d A dye

5. Use

d cdye

A dye

a set at

to convert

A dye c dye

Rate law

dye m

dye m =k p

Since c bleach c dye c bleach 0 so

,

k

d c dye

r=

=

dt

where k p is the pseudo-rate constant

dc

=k p

dt

dc=k p dt

m=0

c

cc0 =k p t

c m=0=k p t +c 0

at time

versus time

m=1

dc

=k p c

dt

dc

=k p dt

c

dc= k p dt

c0

c0

1c dc=k p dt

log ( c)log (c 0)=k p t

k t

c m=1=c 0 e

p

m=2

dc

2

=k p c

dt

dc

=k p dt

c2

c

t

1

c 2 dc=k p dt

c

0

1 1

=k p t

c0 c

1

c m=2=

k P t+c 01

0

c 0 and

since

| || || |

d 2 c m=2

d t2

If

If

is linear

If

d 2 cm =1

>

d t2

>

d 2 c m=0

dt2

c vs. t is linear, then reaction is of the zeroth order since c m=0 is linear

log(c) vs. t is linear, then reaction is of the first order since log ( cm =1 )=k p t+ log (c 0 )

1

c

vs.

Use pipet to deliver 9.00 - 9.90 mL of dye (Yellow 6, 3.4 10-5 M) into vial

Move vial into spectrophotometer

Drop magnetic bar into vial

Use syringe to deliver 1.00 - 0.10 mL bleach (0.090 or 0.180 M) into the vial in order to make

volume 10.00 mL

Immediately cover vial with black lid to start measurement

Print kinetic trace out and show TA

Record all data (absorbance-time data points) on feedback form and hand it in to TA

Step 2: Getting information from a kinetic trace (order and pseudo-rate constant)

Since log(c) vs. t is linear, rate is of order 1

By Beers Law, A c and since log(c)=k p t +log(c 0 ) then log( A)=k p t +log ( A 0)

Compute

k p =log(

A1

)/t using kinetic trace

Ao 1

Repeat procedure from step 1, this time using 0.180 M bleach instead of 0.090 M bleach

Since reaction rate doubles, r=k [dye ][bleach] so n=1

Step 4: Putting it all together

Convert

A c

log 10(

I

)= A= lc , where

I0

is substance &

Re-write A= lc as A=mc , where m is slope of A vs. c graph

(representing l )

Obtain slope by measuring A dye with a set of different c dye

E.g. for a concentration of 80%, pour 8 mL dye and 2 mL water

Since

100

)

c 100

A

, as well as r 1 at any t 1 , which

m

is r=k ' [bleach] where [bleach] is some c 1 at its corresponding t 1

1

Recommended to use points (c 1 , A1 ) ,(c 2 , A2 ) , where c 2> c 1 and A 2 A 1

2

c 1 at any

A 1 using c=

Experimental Procedure

1. Perform test run of bleaching using ~10 mL dye & ~1-2 mL bleach, observing reaction & rate

2. Obtain kinetic traces (absorbance-time graphs) by making 6 10.0 mL dye-0.25 M bleach solutions

(aim for 90% dye concentration, 9.00 mL dye)

a. Pipet dye into vial

b. Move into spectrophotometer

c. Drop magnetic bar into vial

d. Syringe bleach into vial

e. Cover with lid

3. Analyze kinetic traces: determine dye order & pseudo-rate constant

a c by Beers law, so

r=k [bleach][dye]=k ' [dye] where

a.

b.

k ' =k [bleach] , so

if A dye vs. t linear, dye order =

0

If dye order = 0, A =k ' t + A 0

if ln ( A dye ) vs. t linear, dye

If dye order = 1, ln( A)=k ' t + ln(A 0 )

order = 1

If dye order = 2, 1/ A=k ' t+1/ A0

1/

A

if

vs. t linear, dye order

dye

=2

4. Repeat step 2, using the doubled concentration this time

5. Determine bleach order by comparing pseudo-rate constants when concentration doubled

a. If k ' remains constant, bleach order = 0

If k ' doubles (increases linearly), bleach order = 1

If k ' quadruples (increases quadratically), bleach order = 2

6. Obtain Beers Law calibration (absorbance-concentration) graph

a. Make 5 10.0 mL aqueous dye solutions, with concentrations 20% apart (e.g. 20%

concentration = 8 mL dye + 2 mL water, etc.)

b. Place each vial in spectrophotometer and record their absorbances at analytical

wavelength

7. Analyze calibration graph: Relate absorbance to concentration

a. Determine slope and convert units of %-1 to M-1 via m(100 / c100 )

b. Use Beers Law to convert any absorbance to concentration via A=mc , where

m= slope

c. Compare reaction rate at two points on absorbance-time graph where one has

the absorbance of the other to verify equation is correct (e.g. if order of dye and bleach is 1,

reaction rate should half)

Glassware

2 beakers (possibly for storing dye & bleach)

6 vials (for kinetic traces & Beers Law calibration)

Serological pipet (0-10 mL)

3 mL syringe with 0.1 mL graduations

MicroLab interface (spectrophotometer & time probes)

Microsoft Excel

Chemicals

160 mL food dye

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