CEE 697K ENVIRONMENTAL REACTION KINETICS Lecture #10 Special - - PowerPoint PPT Presentation

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CEE 697K ENVIRONMENTAL REACTION KINETICS Lecture #10 Special - - PowerPoint PPT Presentation

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Updated: 17 October 2013 CEE697K Lecture #10 1 Print version CEE 697K ENVIRONMENTAL REACTION KINETICS Lecture #10 Special Topics: DCP in Water Primary Literature (e.g., Guthrie & Cossar, 1986) Introduction David A. Reckhow Guthrie

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SLIDE 1

CEE 697K

ENVIRONMENTAL REACTION KINETICS

Introduction

David A. Reckhow

CEE697K Lecture #10 1

Updated: 17 October 2013

Print version

Lecture #10

Special Topics: DCP in Water

Primary Literature (e.g., Guthrie & Cossar, 1986)

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SLIDE 2

Guthrie

 J. Peter Guthrie

 Department of Chemistry

Western University, London, Ontario, Canada, N6A 5B7

 B.Sc.

 Univ. Western Ontario

 PhD Chemistry, 1968  Harvard University

 DECARBOXYLATION AND ENAMINE

FORMATION: MODEL SYSTEMS FOR ACETOACETATE DECARBOXYLASE

 By James Peter Guthrie

 Princeton Univ.  1970, Faculty, Western

University

David A. Reckhow

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CEE697K Lecture #10 Guthrie, J. P. and J. Cossar (1986). "The Chlorination of Acetone - A Complete Kinetic Analysis." Canadian Journal of Chemistry-Revue Canadienne De Chimie 64(6): 1250-1266.

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SLIDE 3

Mechanisms: Haloform Reaction

David A. Reckhow

CEE690K Lecture #09

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 Chlorine + acetone

 Morris & Baum, 1978  Brezonik, 1994

Pg 240-241

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SLIDE 4

Haloform reaction: initial step

David A. Reckhow

CEE690K Lecture #09

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 Three potential pathways to enolate

 Reaction with water (KO), hydroxide (KOH), and proton (KH)

 kf=KO+KOH[OH-]+KH[H+]  For acetone, the OH pathway dominates above pH 5.5

What is kr?

] [ ] ][ [ HA A H k k K

r f a − +

= =

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SLIDE 5

Guthrie & Cossar Pathway

David A. Reckhow

CEE697K Lecture #10

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 Scheme 1

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SLIDE 6

David A. Reckhow

CEE697K Lecture #10

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 a

Hydrolysis of 1,1-DCP

The product

The many forms of 1,1-DCP

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SLIDE 7

DCP equilibria I

David A. Reckhow

CEE697K Lecture #10

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 Bell K’s

pH

2 4 6 8 10 12 14

Alpha

0.0 0.2 0.4 0.6 0.8 1.0 1.2 H+ alpha E alpha Q alpha L alpha 5

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SLIDE 8

DCP equilibria II

David A. Reckhow

CEE697K Lecture #10

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 Bell K’s

pH

2 4 6 8 10 12 14

Alpha

1e-8 1e-7 1e-6 1e-5 1e-4 1e-3 1e-2 1e-1 1e+0 1e+1 H+ alpha E alpha Q alpha L alpha 5

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SLIDE 9

DCP equilibria III

David A. Reckhow

CEE697K Lecture #10

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 Guthrie K’s

pH

2 4 6 8 10 12 14

Alpha

0.0 0.2 0.4 0.6 0.8 1.0 1.2 H+ alpha E alpha Q alpha L alpha 5

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SLIDE 10

DCP equilibria IV

David A. Reckhow

CEE697K Lecture #10

10

 Guthrie K’s

pH

2 4 6 8 10 12 14

Alpha

1e-8 1e-7 1e-6 1e-5 1e-4 1e-3 1e-2 1e-1 1e+0 1e+1 H+ alpha E alpha Q alpha L alpha 5

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SLIDE 11

Loss of intermediates in lab water

David A. Reckhow

CEE690K Lecture #09

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 21C, ultrapure

water

 (Nikolaou et al.,

2001)

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SLIDE 12

David A. Reckhow

CEE697K Lecture #10

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 chlorine

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SLIDE 13

David A. Reckhow

CEE697K Lecture #10

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 a

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SLIDE 14

Model

David A. Reckhow

CEE697K Lecture #10

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 Guthrie model for 1,1-DCP degradation

pH

4 5 6 7 8 9 10 11 12 13 14

Half-Life (hrs)

0.0001 0.001 0.01 0.1 1 10 100 1000 Chlorine Hydrolysis

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SLIDE 15

LFER Analysis

David A. Reckhow

CEE697K Lecture #10

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 Baiyang Chen analysis  pH 7-7.5  20-25C  Predicted hydrolysis

rate constant for 1,1- DCP is 10-1.66 hr-1

 Half-life of 31.7 hr

 6.1 x 10-6 sec-1  (Chen, 2011).  Data point estimated from

Nikolaou et al., 2001

Chen, B. Y. "Hydrolytic Stabilities of Halogenated Disinfection Byproducts: Review and Rate Constant Quantitative Structure- Property Relationship Analysis." Environmental Engineering Science 28(6): 385-394.

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SLIDE 16

Comparison with Chen 2001

David A. Reckhow

CEE697K Lecture #10

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 Guthrie model for 1,1-DCP degradation

pH

4 5 6 7 8 9 10 11 12 13 14

Half-Life (hrs)

0.0001 0.001 0.01 0.1 1 10 100 1000 Chlorine Hydrolysis

Chen, 2011

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SLIDE 17

Loss in water heaters

David A. Reckhow

CEE690K Lecture #09

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 Liu et al.,

2013

 In review

Reaction Time (hr) 20 40 60 80 100 120 CP (฀g/L) 0.0 0.1 0.2 0.3 0.4 0.5 0.6 No heating 6 hrs incubation+heating 24 hrs incubation+heating 48 hrs incubation+heating 72 hrs incubation+heating 96 hrs incubation+heating Reaction Time (hr) 20 40 60 80 100 120 TCP (฀g/L) 0.0 2.0 4.0 6.0 8.0 No heating 6 hrs incubation+heating 24 hrs incubation+heating 48 hrs incubation+heating 72 hrs incubation+heating 96 hrs incubation+heating Reaction Time (hr) 20 40 60 80 100 120 DCAN (฀g/L) 0.0 0.5 1.0 1.5 2.0 2.5 No heating 6 hrs incubation+heating 24 hrs incubation+heating 48 hrs incubation+heating 72 hrs incubation+heating 96 hrs incubation+heating Reaction Time (hr) 20 40 60 80 100 120 1,1-DCP (฀g/L)

0.0 0.5 1.0 1.5 2.0 2.5 3.0

No heating 6 hrs incubation+heating 24 hrs incubation+heating 48 hrs incubation+heating 72 hrs incubation+heating 96 hrs incubation+heating

a b c d

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SLIDE 18

Profile of 1,1-DCP in Water Systems

David A. Reckhow

CEE697K Lecture #10

18  1,1-Dichloropropanone concentrations compared to the corresponding

TTHM concentration for all samples

Chloroform (฀g/L)

20 40 60 80 100 120 140

1,1-dichloropropanone (฀g/L)

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 6.0 8.0 San Francisco Jan(Cl2/NH4Cl) Charleston(ClO2/ NH4Cl) San Francisco Apr (Cl2/NH4Cl) Ann Arbor(O3/NH4Cl) East Bay( Cl2/NH4Cl) Cincinnati(Cl2) Minneapolis (NH4Cl/NH4Cl) Monroe(O3/Cl2) Wyoming( Cl2/Cl2) Pinellas County(Cl2/Cl2) Pinellas County(Cl2/NH4Cl) Knoxville(ClO2/Cl2)

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SLIDE 19

David A. Reckhow

CEE697K Lecture #10

19  1,1-Dichloropropanone concentrations compared to the corresponding

TTHM concentration for all samples: focus on free chlorine plants

Chloroform (฀g/L)

20 40 60 80 100 120

1,1-dichloropropanone (฀g/L)

0.0 0.2 0.4 0.6 0.8 1.0 San Francisco Jan(Cl2/NH4Cl) Charleston(ClO2/ NH4Cl) San Francisco Apr (Cl2/NH4Cl) Ann Arbor(O3/NH4Cl) East Bay( Cl2/NH4Cl) Cincinnati(Cl2) Minneapolis (NH4Cl/NH4Cl) Monroe(O3/Cl2) Wyoming( Cl2/Cl2) Pinellas County(Cl2/Cl2) Pinellas County(Cl2/NH4Cl) Knoxville(ClO2/Cl2) Monroe Cincinnati Wyoming Pinellas County

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SLIDE 20

Profile of TCP in water systems

David A. Reckhow

CEE690K Lecture #09

20  1,1,1-Trichloropropanone concentrations compared to the corresponding

TTHM concentration for all samples

Chloroform (฀g/L)

20 40 60 80 100 120 140

1,1,1- trichloropropanone (฀g/L)

1 2 3 4 5 San Francisco Jan(Cl2/NH4Cl) Charleston(ClO2/ NH4Cl) San Francisco Apr (Cl2/NH4Cl) Ann Arbor(O3/NH4Cl) East Bay( Cl2/NH4Cl) Cincinnati(Cl2) Minneapolis (NH4Cl/NH4Cl) Monroe(O3/Cl2) Wyoming( Cl2/Cl2) Pinellas County(Cl2/Cl2) Pinellas County(Cl2/NH4Cl) Knoxville(ClO2/Cl2) Monroe Pinellas Co. Knoxville

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SLIDE 21

Lab 2

David A. Reckhow

CEE697K Lecture #10

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 15 Oct 2013 experiment

Reaction Time (sec)

100 200 300

Absorbance at 292 nm

0.0 0.1 0.2 0.3 Time (s) vs Abs

absinf = 0.012

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SLIDE 22

Lab 2

David A. Reckhow

CEE697K Lecture #10

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 1st order plot

Reaction Time (sec)

100 200 300

Ln (Abs-Abs฀฀

  • 6
  • 5
  • 4
  • 3
  • 2
  • 1

Time (s) vs ln abs-absinf Plot 1 Regr b[1]฀-0.0128851211

absinf = 0.012

K = 46 hr-1

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SLIDE 23

Lab 2

David A. Reckhow

CEE697K Lecture #10

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 2nd order plot

Reaction Time (sec)

100 200 300

1/(Abs-Abs฀฀

50 100 150 200 250 300 Time (s) vs 1/(abs-absinf) Plot 1 Regr

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SLIDE 24

David A. Reckhow

CEE697K Lecture #10

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 Guthrie model

pH

4 5 6 7 8 9 10 11 12 13 14

Half-Life (hrs)

0.0001 0.001 0.01 0.1 1 10 100 1000 Chlorine Hydrolysis

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SLIDE 25

David A. Reckhow

CEE697K Lecture #10

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 To next lecture