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bleach n

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

Objective: determine rate law by measuring r using different c each time


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

(absorbance: colour intensity)

1. Monitor A dye vs. t during bleach reaction (kinetic trace)


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

dr
, then perform
d c bleach

3. Use research questions, hypotheses & experiment design to determine


experiment to determine m
4. Use Beers Law to convert

analytical
d A dye
5. Use
d cdye

A dye c dye : since c A , measure

A dye

of each dye dilution in

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

Concentration of the dye

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

(given initial concentration

k p ) for a first, second, and third order reaction ( m=0, 1,2 :


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

, reactions with larger orders have a larger change in reaction rate

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.

is linear, then reaction is of the second order since

c m=2 1=k p t+ c 01 is linear

Step 1: Making a kinetic trace


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

Step 3: Determine the effect of bleach on the reaction


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

using Beers Law:

log 10(

I
)= A= lc , where
I0

is substance &

wavelength-specific constant, & l is length light travels through sample


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

m has unit %-1, convert to M-1: m(

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

Now possible to calculate

c 1 at any

A 1 using c=

to verify that order you determined matches up with rate


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

1 graduated cylinder (for test run)


2 beakers (possibly for storing dye & bleach)
6 vials (for kinetic traces & Beers Law calibration)

Instruments & measuring devices


Serological pipet (0-10 mL)
3 mL syringe with 0.1 mL graduations
MicroLab interface (spectrophotometer & time probes)
Microsoft Excel
Chemicals

8.0 mL ~0.25 M NaOCl (bleach)

6.0 mL ~0.50 M NaOCl


160 mL food dye