1

SUPPLEMENTARY INFORMATION

Precision measurement of the growth rate and mechanism of ibuprofen {001}

and {011} as a function of crystallization environment

T. T. H. Nguyen, R. B. Hammond, K. J. Roberts*

Institute of Particle Science and Engineering, Institute of Process Research and Development,

School of Process, Environmental and Materials Engineering, University of Leeds, Leeds, LS2

9JT, Leeds

I. Marziano, G. Nichols

Pfizer Worldwide Research and Development, Sandwich, CT13 9NJ, UK

(*) Corresponding author’s email: K.J.Roberts@leeds.ac.uk

Abstract

The crystallisation of ibuprofen under diffusion-limited conditions measured as a function of

supersaturation, solvent and reactor scale is described in the main paper and in this

supplementary material some additional information is provided. This comprises:

• Details concerning the raw ATR UV/Vis spectra collected and the associated calibration

used to determine the concentration of ibuprofen in 95% ethanol/water, ethyl acetate, and

acetonitrile solvents as a function of temperature (section S1.1)

• Details of the gravimetric calculations used for the determination of the solubility of

ibuprofen in toluene solutions (section S1.2)

• All the raw in-situ microscopy image data and its associated analysis which underpin the

determination of face-specific growth rates as presented in the main paper (section S2).

Electronic Supplementary Material (ESI) for CrystEngComm.This journal is © The Royal Society of Chemistry 2014

2

S1. Data related to solubility determination in 95% ethanol/water, ethyl acetate, and

acetonitrile solvents by ATR UV/Vis spectroscopy

S1. 1 ATR UV/Vis method development

The Beer-Lambert law states that the absorbance of a solution is directly proportional to the

concentration of the absorbing species in the solution and the path length. Hence, ATR UV/Vis

spectroscopy can be employed to determine the concentration of ibuprofen in a solution for a

fixed path length. The calibration curve of ibuprofen was determined by measuring absorbance

versus a range of concentrations using the specific absorbance peak of ibuprofen at 264 nm

(Figure S1).

0

0.02

0.04

0.06

0.08

0.1

0.12

250 260 270 280 290 300

Ab

sorb

ance

Wavelength (nm)

(a)

0.6g/ml0.8g/ml1g/ml1.2g/ml1.4g/ml

0

0.02

0.04

0.06

0.08

250 260 270 280 290 300

Ab

sorb

ance

Wavelength (nm)

(b)

0.4g/ml0.6g/ml0.8g/ml1.0g/ml

3

Figure S1 Spectra of ibuprofen in 95% ethanol/water (a), ethyl acetate (b) and acetonitrile (c)

showing absorbance increase with increasing concentration of solutions and from these

absorbances at 264 nm and known concentrations, calibration curves (d) were obtained.

Table S1 Calibration line of ibuprofen in 95% ethanol/water, ethyl acetate and acetonitrile at

temperature from 15-35oC

Solvents Calibration line

95% Ethanol/Water

Ethyl acetate

Acetonitrile

y = 0.0818x – 0.0172

y = 0.0786x – 0.0034

y = 0.0503x + 0.0017

0

0.005

0.01

0.015

0.02

0.025

250 260 270 280 290 300

Ab

sorb

ance

Wavelength (nm)

(c)

0.1g/ml

0.2g/ml

0.3g/ml

0.4g/ml

0

0.02

0.04

0.06

0.08

0.1

0.12

0 0.4 0.8 1.2

Ab

sorb

ance

Concentration (g/ml)

(d)

AcetonitrileEthyl acetateEthanol

4

Table S1 shows the regression fits obtained from the calibration curves from which the solubility

of ibuprofen in these 3 solvents over the temperature range 15-35oC was determined.

Figure S2 An example of spectra of ibuprofen in ethyl acetate at 15, 20, 25, 30 and 35°C

showing absorbances increase with increasing temperature of saturated solutions and λmax does

not shift with temperature

Spectroscopic exanimation of the ibuprofen solutions in the UV region revealed a strong

absorbance maximum at about 264 nm. The λmax was not found to shift even in different

solvents and concentration nor even as a function of temperature.

The ATR-UV/Vis spectroscopy calibration shows a linear correlation between UV/Vis

absorbance intensity and the solute concentration for different concentrations of ibuprofen in

-0.01

0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

250 255 260 265 270 275 280 285 290 295 300

Ab

sorb

ance

Wavelength (nm)

5

solvents. For a constant solution concentration, absorbance was found to be quite constant as a

function of a temperature, as shown in Figure S2.

S1.2 Data related to solubility determination toluene solvents by gravimetric

methods

Table S2 provides the raw gravimetric data together with the associated determination of the

solubility of ibuprofen in toluene solutions over the temperature range from 15-35°C was

determined.

Table S2 Solubility of ibuprofen in toluene solutions over the temperature range from 15-35°C

T(°C) 15 20 25 30 35

Sample 1 0.367 0.46 0.588 0.75 0.913

Sample 2 0.366 0.46 0.591 0.753 0.974

Sample 3 0.588 0.936

C(g/g) 0.367 0.46 0.589 0.7515 0.941

STDEV 0.00173 0.00212 0.03080

6

S2. Crystal growth rate measurement in the 0.5ml cuvette cell and the 15ml

jacketed vessel

The data presented comprises plots of growth rate versus time for the {011} and {001} faces for

all the crystals measured together with a representative image set for one of these crystals.

S2.1 Data from the 0.5ml cuvette cell

S2.1.1 95% Ethanol/Water Solutions

σ = 1.15

y = 21.7x + 213.5y = 22.5x + 232.67

y = 19.3x + 347.4

y = 22.6x + 274.7

y = 21.7x + 142.9

0

100

200

300

400

500

0 2 4 6 8 10

Dis

tan

ce f

rom

cen

ter

to f

ace

(μm

)

Time (mins)

The {011} face at σ = 1.15

y = 12.2x + 130.35

y = 14.3x + 130.33

y = 10.9x + 205.7y = 14.8x + 173

y = 14.1x + 98.65

0

100

200

300

0 2 4 6 8 10

Dis

tanc

e fr

om c

ente

r to

fac

e (μ

m)

Time (mins)

The {001} face at σ = 1.15

7

σ = 0.89

σ = 0.79

y = 14.0x + 182.9

y = 12.5x + 152.4y = 14.5x + 157.7

y = 16.1x + 404.57

0

200

400

600

800

0 5 10 15 20 25

Dis

tanc

e fr

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fac

e (μ

m)

Time (mins)

The {011} face at σ = 0.89

y = 5.7x + 93.9

y = 5.8x + 78.6y = 5.9x + 83.8

y = 7.4x + 191.2

0

100

200

300

400

0 5 10 15 20 25

Dis

tanc

e fr

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fac

e (μ

m)

Time (mins)

The {001} face at σ = 0.89

y = 13.5x + 156.8

y = 9.5x + 151.6

y = 12.5x + 529.4

y = 10.7x + 237.1

y = 11.2x + 199.4

0

200

400

600

800

0 10 20 30 40

Dis

tanc

e fr

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fac

e (μ

m)

Time (mins)

The {011} face at σ = 0.79

y = 4.9x + 79.2

y = 4.4x + 71.2

y = 5.1x + 295.4

y = 4.3x + 98.4

y = 4.1x + 90.4

0

100

200

300

400

500

0 10 20 30 40

Dis

tan

ce f

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cen

ter

to f

ace

(μm

)

Time (mins)

The {001} face at σ = 0.79

8

σ = 0.66

S2.1.2 Ethyl Acetate Solutions

σ = 1.12

y = 11.2x + 80.9

y = 10.3x + 82.6

y = 6.9x + 188.6

y = 7.6x + 459.9

y = 6.6x + 379.8

0

100

200

300

400

500

600

700

0 5 10 15 20 25

Dis

tan

ce f

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cen

ter

to f

aces

(μ

m)

Time (mins)

The {011} face at σ = 0.66

y = 4.4x + 124.0

y = 2.5x + 85.2

y = 4.0x + 35.6y = 3.6x + 33.1

y = 3.5x + 103.6

0

50

100

150

200

250

0 5 10 15 20 25

Dis

tan

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cen

ter

to f

ace

(μm

)

Time (mins)

The {001} face at σ = 0.66

y = 66.5x + 270.5y = 60x + 198.8

y = 72.2x + 342.4

y = 62.8x + 310.8

y = 55.3x + 428.4

y = 50.9x + 289.6

0

200

400

600

800

0 1 2 3 4 5 6

Dis

ntan

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ace

(μm

)

Time (mins)

The {011} face at σ = 1.22

y = 9.7x + 62.5

y = 10.8x + 66.3

y = 9.3x + 67.5y = 15.4x + 74.9

y = 14.7x + 74.15

y = 13.2x + 52.2

0

40

80

120

160

200

0 1 2 3 4 5 6

Dis

tanc

e fr

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fac

e (μ

m)

Time (mins)

The {001} face at σ = 1.22

9

σ = 1.06

σ = 0.97

y = 63x + 481.67

y = 47.7x + 351.8

y = 55.4x + 456.4

y = 47.6x + 147.8

y = 48.1x + 555.1

y = 48.7x + 401.4

y = 56.7x + 251.5

0

100

200

300

400

500

600

700

800

0 1 2 3 4 5 6

Dis

tanc

e fr

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fac

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m)

Time (mins)

The {011} face at σ = 1.06

y = 9.3x + 43.75

y = 10x + 79.167 y = 9.8x + 74

y = 10.4x + 79.3

y = 9.9x + 25.4

y = 8.9x + 78.5

y = 9.6x + 41.75

0

20

40

60

80

100

120

140

0 1 2 3 4 5 6

Dis

tan

ce f

rom

cen

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to f

ace

(μm

)

Time (mins)

The {001} at σ = 1.06

y = 54.6x + 201.1

y = 47.6x + 594.7

y = 47.7x + 725.9

y = 52.1x + 171

y = 45.1x + 111.5y = 46x + 122

0

200

400

600

800

1000

1200

0 2 4 6 8

Dis

tanc

e fr

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fac

e (μ

m)

Time (mins)

The {011} face in at σ = 0.97

y = 8.7x + 37.55

y = 9.5x + 116.65

y = 8.4x + 34.8

y = 7.4x + 20.917y = 7.3x + 24.333

0

50

100

150

200

0 2 4 6 8

Dis

tan

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cen

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to f

ace

(μm

)

Time (mins)

The {001} face at σ = 0.97

10

σ = 0.85

σ = 0.76

y = 39.1x + 159.49

y = 41.8x + 551.9

y = 37.9x + 1049.3

y = 42x + 631.5y = 48.7x + 243.76

y = 43.5x + 143.17

y = 43.1x + 642.62

y = 43.9x + 415.4

0

200

400

600

800

1000

1200

1400

0 5 10 15

Dis

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cen

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(μm

)

Time (mins)

The {011} face at σ = 0.85

y = 5.9x + 26.206

y = 5.7x + 72.2

y = 6.6x + 72.95

y = 6.8x + 46.952

y = 6x + 22.667

y = 6.5x + 70.7

0

40

80

120

160

200

0 5 10 15

Dis

tanc

e fr

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fac

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m)

Time (mins)

The {001} face at σ = 0.85

y = 42.8x + 174.6

y = 34.5x + 372.5y = 37.6x + 323.5

y = 36.3x + 396.6

y = 34.7x + 757.6

y = 38.9x + 238.59

0

200

400

600

800

1000

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1400

0 5 10 15 20

Dis

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(μm

)

Time (mins)

The {011} face at σ = 0.76

y = 4.8x + 29

y = 4.2x + 61.85 y = 4.1x + 48.167

y = 4.8x + 58.2

y = 3.3x + 87.45

y = 5.0x + 34.008

0

20

40

60

80

100

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140

0 5 10 15 20

Dis

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m)

Time (mins)

The {001} face at σ = 0.76

11

σ = 0.69

σ = 0.54

y = 29.3x + 315.9y = 31.4x + 232

y = 30.8x + 292

y = 31.6x + 237.2

y = 33.6x + 143.5

0

400

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1600

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Dis

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(μm

)

Time (mins)

The {011} face at σ = 0.69

y = 3.3x + 36.8y = 4.2x + 27.3

y = 3.4x + 30.8

y = 3.2x + 22y = 3.2x + 22.9

0

40

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120

160

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Dis

tanc

e fr

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fac

es (μ

m)

Time (mins)

The {001} face at σ = 0.69

y = 18.9x + 293.5

y = 16.6x + 310.1

y = 20.7x + 175.4

y = 16.0x + 176.9

y = 15.9x + 652.6

0

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1200

0 5 10 15 20 25 30

Dis

tanc

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fac

e (μ

m)

Time (mins)

The {011} face at σ = 0.54

y = 2.2x + 36.839

y = 1.6x + 30

y = 1.9x + 18.81

y = 1.7x + 22.3

y = 1.4x + 70.833

0

40

80

120

0 5 10 15 20 25 30

Dis

tanc

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m)

Time (mins)

The {001} face at σ = 0.54

12

S2.1.3 Acetonitrile Solutions

σ = 1.31

σ = 1.12

y = 109.2x + 511.17

y = 113.4x + 711.4

y = 103.9x + 320.4

y = 110x + 436.5

y = 99.5x + 418.17

y = 136x + 589

0

200

400

600

800

1000

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0 1 2 3 4 5

Dis

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cen

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(μm

)

Time (mins)

The {011} at σ = 1.31

y = 13.4x + 83.75

y = 17.3x + 102.05

y = 16.1x + 35.55

y = 12.5x + 75.667y = 17.3x + 58.3

0

40

80

120

160

200

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Dis

tan

ce f

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cen

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to f

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(μm

)

Time (mins)

The {001} face at σ = 1.31

y = 90.4x + 554

y = 99.6x + 267.19

y = 94x + 606.67

y = 96.5x + 154.4

y = 93.5x + 501.6

y = 80.5x + 536.71

0

200

400

600

800

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1200

0 1 2 3 4 5 6

Dis

tanc

e fr

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fac

e (μ

m)

Time (mins)

The {011} face at σ = 1.12

y = 10.5x + 51.5 y = 13x + 36

y = 10.5x + 75.5y = 11.8x + 81.571

y = 7.9x + 33.8

0

20

40

60

80

100

120

140

160

0 1 2 3 4 5 6Dis

tanc

e fr

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fac

e (μ

m)

Time (mins)

The {001} face at σ = 1.12

13

σ = 1.03

σ = 0.93

y = 77.0x + 209.9

y = 70.2x + 839.2y = 98.4x + 841.9

y = 67.7x + 416.17

y = 88.2x + 830.83y = 77.8x + 1033.3

0

200

400

600

800

1000

1200

1400

0 2 4 6 8

Dis

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fac

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m)

Time (mins)

The {011} face at σ = 1.03

y = 7.7x + 21.6

y = 10.7x + 73.9

y = 5.9x + 51.4

y = 6.3x + 58.833y = 6.3x + 84.05

0

20

40

60

80

100

120

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Dis

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cen

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to f

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(μm

)

Time (mins)

The {001} face at σ = 1.03

y = 71x + 839.67

y = 55.7x + 263.4y = 55.7x + 263.4

y = 61.3x + 855.3

y = 55.5x + 369.5

0

200

400

600

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1400

0 1 2 3 4 5 6

Dis

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e fr

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fac

e (μ

m)

Time (mins)

The {011} face at σ = 0.93

y = 5.5x + 57.667

y = 4.8x + 35.35

y = 4.6x + 38.85

y = 5.1x + 100.1

y = 4.9x + 33.15

0

20

40

60

80

100

120

140

0 1 2 3 4 5 6

Dis

tan

t fr

om c

net

er t

o fa

ce (μ

m)

Time (mins)

The {001} face at σ = 0.93

14

σ = 0.79

S2.1.4 Toluene Solutions

σ = 0.86

y = 49.8x + 326.4

y = 48x + 329.8

y = 48.7x + 329.2

y = 60.5x + 282.76

y = 50.3x + 220.81

0

200

400

600

800

1000

0 2 4 6 8 10 12

Dis

tan

ce f

rom

cen

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to f

ace

(μm

)

Time (mins)

The {011} face at σ = 0.79

y = 4.8x + 18.2

y = 3.4x + 40.3

y = 3.3x + 37.2y = 3.2x + 39.3

y = 3.7x + 24.381

y = 2.9x + 16.19

0

20

40

60

80

0 2 4 6 8 10 12

Dis

tan

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rom

cen

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ace

(μm

)

Time (mins)

The {001} face at σ = 0.79

y = 38.9x + 351.8

y = 37.4x + 354.7

y = 38.5x + 354.0

y = 29.2x + 581.4

y = 29.7x + 211.3

y = 32.6x + 1041.6

0

200

400

600

800

1000

1200

1400

0 5 10 15 20

Dis

tanc

e fr

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fac

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m)

Time (mins)

The {011} face at σ = 0.86

y = 3.3x + 37.0

y = 3.0x + 35.1

y = 3.1x + 35.8

y = 2.0x + 15.2

y = 3.1x + 79.4

y = 3.4x + 74.1

0

20

40

60

80

100

120

0 5 10 15 20

Dis

tanc

e fr

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m)

Time (mins)

The {001} face at σ = 0.86

15

σ = 0.78

σ = 0.70

y = 27.5x + 629.9

y = 31x + 239.6

y = 34.4x + 317.1y = 30.5x + 524.6

y = 29.0x + 509.3

0

200

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Dis

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m)

Time (mins)

The {011} face at σ = 0.78

y = 2.1x + 45.9

y = 2.4x + 22

y = 2.5x + 23.2y = 2.2x + 36.4

y = 2.2x + 43

0

20

40

60

80

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Dis

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e fr

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m)

Time (mins)

The {001} face at σ = 0.78

y = 28.9x + 534.6

y = 25.6x + 427.3

y = 27x + 205.6

y = 30.8x + 438.6y = 26.4x + 400.4

y = 28.9x + 306.2

0

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1600

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Dis

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(μm

)

Time (mins)

The {011} face at σ = 0.7

y = 2.0x + 25.9

y = 1.7x + 22.8

y = 1.9x + 29.9

y = 1.5x + 56.9

y = 2.0x + 23

0

20

40

60

80

100

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Dis

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m)

Time (mins)

The {001} face at σ = 0.7

16

S2.2 Data from the 15ml jacketed vessel

S2.2.1 95% Ethanol /Water Solutions

σ = 1.15

σ = 0.97

y = 22.1x + 163

y = 25.6x + 198.8

y = 22.4x + 155

y = 31.5x + 186.4y = 21.6x + 272.8

0

100

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500

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Dis

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m)

Time (mins)

The {011} face at σ = 1.15

y = 12.9x + 113

y = 14.4x + 119.5

y = 12.6x + 98.7

y = 12.8x + 125.7

y = 13.4x + 158.2

0

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250

300

0 2 4 6 8

Dis

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e fr

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r fa

ce (μ

m)

Time (mins)

The {001} face at σ = 1.15

y = 22.5x + 174y = 25.8x + 146.8

y = 27x + 157.33

y = 26.6x + 280.7

y = 20.9x + 289.8

y = 25.5x + 246.3y = 28.3x + 238.2

0

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500

0 2 4 6

Dis

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m)

Time (mins)

The {011} face at σ = 0.97

y = 17.8x + 341.5

y = 14x + 112.7y = 14.8x + 99.2

y = 16x + 103.3

y = 13.3x + 186.5

y = 15.8x + 149.8

0

100

200

300

400

500

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Dis

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m)

Time (mins)

The {001} face at σ = 0.97

17

σ = 0.89

σ = 0.66

y = 16.6x + 335.4

y = 16.9x + 592.6

y = 16.1x + 182.9

y = 16.4x + 426

y = 18.3x + 609.4

0

200

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1000

0 2 4 6 8 10 12Dis

tanc

e fr

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fac

e (μ

m)

Time (mins)

The {011} face at σ = 0.89

y = 8.1x + 157.3

y = 6.2x + 234.1

y = 7.2x + 95.9

y = 6.6x + 214.5

y = 7.9x + 310.46

0

100

200

300

400

500

0 2 4 6 8 10 12

Dis

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Time (mins)

The {001} face at σ = 0.89

y = 11.3x + 232.33

y = 12.2x + 204.47

y = 10.3x + 617.8

y = 9.9x + 358.57

y = 11.7x + 336.4

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Time (mins)

The {011} face at σ = 0.66

y = 3.4x + 78

y = 4.2x + 74.731

y = 4.2x + 226.8

y = 3.6x + 156.43y = 4.5x + 156.4

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The {001} face at σ = 0.66

18

S2.2.2 Ethyl Acetate Solutions

σ = 1.22

σ = 1.06

y = 67.3x + 422.1y = 59.5x + 416.4

y = 68.5x + 397.67y = 65.2x + 355.4

y = 70.6x + 644.6

y = 63.5x + 379y = 67.1x + 337.8

y = 61.7x + 388.8

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The {011} face at σ = 1.22

y = 15.8x + 97.6

y = 13.6x + 86.2

y = 12.3x + 89.2y = 12.7x + 88.2

y = 13.7x + 96.5y = 15.3x + 90.0

y = 14.1x + 76.4

y = 13.2x + 90.8

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Time (mins)

The {001} face at σ = 1.22

y = 53.8x + 499

y = 58.6x + 241.1y = 56.5x + 254.5

y = 59.1x + 231.7

y = 58.1x + 133

y = 62.1x + 207.8

y = 62.3x + 245.1

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The {011} face at σ = 1.06

y = 12.4x + 114.1

y = 12.7x + 56.9

y = 12.9x + 57.4 y = 12.9x + 56.5

y = 13.0x + 59.6

y = 12.2x + 52.6

y = 11.8x + 52.8

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The {001} face at σ = 1.06

19

σ = 0.97

σ = 0.85

y = 54.3x + 283.8

y = 52.1x + 402.1

y = 51.3x + 582.3y = 50.1x + 508.6

y = 55.3x + 558.1

y = 55.1x + 220.8

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The {011} face at σ = 0.97

y = 10.8x + 55.7

y = 10.1x + 78.4

y = 9.4x + 113.4

y = 11.4x + 102.7y = 9.2x + 113.4

y = 9.8x + 48.2

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Time (mins)

The {001} face at σ = 0.97

y = 51.9x + 464.2y = 51.8x + 447.5

y = 41.3x + 245.1y = 46x + 255.3

y = 46.2x + 268.3y = 44.9x + 280.8

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Time (mins)

The {011} face at σ = 0.85

y = 7.1x + 75.1

y = 5.8x + 37.8

y = 6.9x + 35.8

y = 5.3x + 31.1

y = 6x + 51

0

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The {001} face at σ = 0.85

20

σ = 0.76

σ = 0.69

y = 44.2x + 328.6

y = 39.7x + 241.1y = 43.7x + 475.2

y = 41.7x + 434.8

y = 39x + 410.3

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Time (mins)

The {011} face at σ = 0.76

y = 6.1x + 50.6

y = 5.1x + 34.9

y = 5.8x + 70.55

y = 6.1x + 69.1y = 5.9x + 56.917

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Time (mins)

The {001} face at σ = 0.76

y = 33.3x + 475.8y = 40.3x + 450.17

y = 38.1x + 338.2y = 38.76x + 328.8

y = 36.6x + 484y = 37.3x + 498.5

y = 31.84x + 246.2

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Time (mins)

The {011} face at σ = 0.69

y = 4.4x + 49.3

y = 4.32x + 40

y = 4.4x + 55.3

y = 2.5x + 25.5

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Time (mins)

The {001} face at σ = 0.69

21

σ = 0.54

S2.2.3 Acetonitrile Solutions

σ = 1.31

y = 20.3x + 329.6

y = 18.6x + 254.4

y = 24.8x + 625.2

y = 16.6x + 480.2y = 15.4x + 429.6

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Time (mins)

The {011} face at σ = 0.54

y = 2.2x + 30.5

y = 1.8x + 24

y = 1.5x + 41.6

y = 1.9x + 51y = 1.9x + 47.2

0

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Time (mins)

The {001} face at σ = 0.54

y = 101.3x + 434.6

y = 121.5x + 473.8y = 115.5x + 614

y = 137.7x + 630.7

y = 120x + 275y = 103x + 283

y = 126x + 454

y = 141.9x + 249.2

y = 128.7x + 271.4

y = 115.2x + 258.8

y = 129x + 263.3

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Time (mins)

The {011} face at σ = 1.31

y = 17.9x + 77.8 y = 18x + 93

y = 14.5x + 42.2

y = 18.3x + 50.5

y = 16.5x + 62.8

y = 16.0x + 51.0

0

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Time (mins)

The {001} face at σ = 1.31

22

σ = 1.12

σ = 1.03

y = 103.5x + 260.2

y = 108.7x + 252.2

y = 102.5x + 263

y = 117x + 527.6

y = 93.0x + 209.7

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Time (mins)

The {011} at σ = 1.12

y = 12.9x + 37.5y = 13.4x + 38.7

y = 12.5x + 39.9

y = 13.8x + 81.3

y = 10.8x + 24.5

0

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Time (mins)

The {001} face at σ = 1.12

y = 83.1x + 526.7

y = 86.2x + 424.4

y = 74.6x + 470.6

y = 78.8x + 344.5

y = 84.8x + 442.5

y = 98.7x + 312.9

y = 91.6x + 301.9

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Time (mins)

The {011} face at σ = 1.03

y = 9.5x + 64.1y = 9.9x + 45.4

y = 9.2x + 48.9

y = 8.1x + 35.6

y = 9.8x + 49.5 y = 9.3x + 33.4

y = 10.2x + 38.1

0

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Time (mins)

The {001} face at σ = 1.03

23

σ = 0.93

σ = 0.75

y = 77.7x + 438.2

y = 70.4x + 326.4

y = 70.7x + 657.1

y = 75.6x + 300.6

y = 70.2x + 323.2

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Time (mins)

The {011} face at σ = 0.93

y = 6.3x + 36.7

y = 5.7x + 25.2

y = 5.9x + 44.6

y = 5.6x + 22.4

y = 5.6x + 24.3

0

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Time (mins)

The {001} face at σ = 0.93

y = 47.5x + 859

y = 57.5x + 342.6

y = 61x + 266.3

y = 62.2x + 316.6y = 60.3x + 392.2

y = 51.8x + 246.2

y = 55.9x + 254.3

y = 54x + 375.5

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Time (mins)

The {011} face at σ = 0.75

y = 2.875x + 40.417

y = 5.7x + 27.143

y = 5.35x + 25.45y = 5.5x + 36

y = 5x + 25.833

y = 5.425x + 25.6y = 4.65x + 24.3

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Time (mins)

The {011} face at σ = 0.75

24

S2.2.4 Toluene Solutions

σ = 1.17

σ = 0.86

y = 46.6x + 360.1

y = 46x + 255.3

y = 41x + 215

y = 43.1x + 186.8

y = 42.3x + 443.2

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Time (mins)

The {011} face at σ = 1.17

y = 4.4x + 36.2y = 5.3x + 35

y = 5.1x + 29.8

y = 5.5x + 27.9y = 4.8x + 54.6

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Time (mins)

The {001} face at σ = 1.17

y = 40.1x + 386.5

y = 40.1x + 386.51

y = 36.6x + 483.6

y = 43.3x + 265.9

y = 37.4x + 239.4

y = 34.5x + 598.1

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Time (mins)

The {011} face at σ = 0.86

y = 3.4x + 38.2

y = 4.4x + 48.9

y = 2.3x + 43.4

y = 4.5x + 32.4

y = 3.2x + 26.9

y = 3.3x + 57

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Time (mins)

The {001} face at σ = 0.86

25

σ = 0.78

σ = 0.70

y = 34.7x + 625.8

y = 38.6x + 659.1

y = 27.9x + 641.7

y = 37.4x + 335.4y = 34.5x + 334.2

y = 28.7x + 217

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Time (mins)

The {011} face at σ = 0.78

y = 3.1x + 46.1

y = 2.9x + 46.6

y = 2.9x + 20.3

y = 2.2x + 35.4

0

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Time (mins)

The {001} face at σ = 0.78

y = 29.1x + 501.8

y = 32.9x + 610.6

y = 31.4x + 313.2

y = 31.4x + 541.6

y = 35.4x + 838.2

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Time (mins)

The {011} face at σ = 0.7

y = 2.2x + 34.2

y = 2.9x + 46.6

y = 2.0x + 26.5

y = 2.9x + 37.5y = 1.9x + 51.8

0

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Time (mins)

The {001} face at σ = 0.7