CHEM 4525 – P-chem lab I Sample lab report

Experiment 1 – Self Diffusion of Acetone

John Doe
Lab partner: Jane Smith

Date completed: September 7, 2015

ABSTRACT:
The room temperature self-diffusion coefficient of acetone was studied using 1H pulsed gradient
spin echo NMR spectroscopic measurements. The self-diffusion coefficient was determined from
the dependence of the NMR signal intensity on the magnetic field gradient. The actual values of the
magnetic field gradient were found from the calibration curve by linear regression. Stejskal-Tanner
equation was used to fit the dependence of the NMR spectral intensity on the field gradient. The
linear fit resulted in the value of D = 5.63 x 10-9 m2s-1. From the Stokes-Einstein equation and the
measured self-diffusion coefficient, the viscosity of acetone was calculated to be  = 0.194 cP. The
effective radius of the acetone molecule was estimated to be 2 Å. These values both compare
favorably with the literature values for the self-diffusion coefficient (D = 4.77 x 10-9 m2s-1) and
viscosity (= 0.307 cP) of acetone.

Introduction
Nuclear magnetic resonance (NMR) measurements in the presence of a known magnetic field
gradient (G) provide a method for measuring the self-diffusion coefficient of liquids.1 The measurement
is based on a NMR gradient echo technique. The diffusion of the molecules in the magnetic field results
in attenuation of the experimental NMR signal, which is proportional to the strength of the applied
gradient. From several measurements of the NMR spectral intensity at different gradient strengths it is
possible to calculate the self-diffusion coefficient.
The equation that describes this phenomenon was first utilized by Stejskal and Tanner:3

A   1 
ln  m    2 D 2     G 2 (1)
 A0   3 

where Am is the measured peak area for the 1H pulsed-field gradient spin-echo (PFG-SE) peak, A0 is the
peak area at zero gradient,  is the magnetogyric ratio for the nucleus of question, D is the diffusion
coefficient,  is the amount of time the gradient is “on”,  is the time between the two gradient pulses, and
G is the magnetic-field strength (commonly symbolized by B nowadays). The magnetogyric ratio is a
constant and is equal to H = 26.7522128 x 107 rad T-1 s-1 for the proton (1H). The times,  and , are set
by the NMR spectroscopist to optimize the experiment and are held constant. For the data that is
provided,  = 21 ms and  = 10 ms. By extracting the peak area at various magnetic field gradient
strengths, one can use eq. (1) to extract the diffusion coefficient, D.
In addition, the Stokes-Einstein equation is used to calculate the viscosity of acetone from the
experimentally determined self-diffusion coefficient. The Stokes-Einstein equation2 is as follows:
CHEM 4525 – P-chem lab I Sample lab report

kT
 , (2)
6rD
where k is the Boltzmann constant, T is the temperature, r is the molecular radius, and D is the self-
diffusion coefficient.

Experimental
Nine separate acetone gradient NMR spectra at 25 °C were provided by the instructor. Calibration
data for the conversion of % magnetic field gradient to the magnetic field gradient in Tesla/meter were
also provided. From the calibration data, the values of the magnetic field gradient (G) in the proper units
(T/m) were first determined, which can be used in Stejskal-Tanner equation (1) for the determination of
the diffusion coefficient. The self-diffusion coefficient of acetone was determined. The provided NMR
spectra peaks as a function of magnetic field gradient were numerically integrated to obtain the total peak
areas Am. These values, along with the peak area at zero gradient A0 were used in the Stejskal-Tanner
equation, which was rearranged as follows:
ln( Am )  ln( A0 )   2 D 2 (  13  )G 2 (3)
to determine the diffusion coefficient from the slope of the linear regression of the plot of ln(Am) with
respect to G2. The linear regression using standard least squares procedures and graphing of data has been
performed in Sigmaplot.

Results
The calibration data for the magnetic field gradient are shown in Table I. A least squares fit (with
constant weights) of a linear function (y = mx) to the calibration data resulted in a converged fit with
r2=0.99868 and produced the fitted parameter m=(4.9  0.1) x10-3 where the errors are the 1 values
determined from the fit. A plot of the fitted function and the calibration data are provided in Fig. 1.

Table I. Magnetic field gradient calibration data.

0.06
% gradient gradient (T/m)
0.00 0.000 0.05
2.0 0.010
0.04
gradient (T/m)

5.0 0.026
7.0 0.034 0.03
10.0 0.049
0.02

0.01

0.00
0 2 4 6 8 10 12
% gradient

Figure 1. A plot of the magnetic field gradient calibration data

(circles) and the fitted linear calibration function.

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CHEM 4525 – P-chem lab I Sample lab report

Representative spectra of the Fourier transformed gradient NMR spectra of acetone at 25 °C are
shown in Figure 2. Examination of the spectra at various magnetic field gradients shows a single peak that
occurs in all spectra, and that the intensity of this peak decreases as the field gradient increases (see Fig.
2). The area of each peak was determined using numerical integration. The results of the numerical
integrations are shown in Table II below.

2e+7

2e+7
intensity

1e+7

5e+6

0
7800 8000 8200 8400 8600

points

Figure 2. An overlay plot of four of 1H gradient NMR spectra used in the analysis for acetone at 25 °C recorded at
2, 6, 10, and 14 % magnetic field gradients. Note that the peak position remains constant, but that the intensity (peak
area) of the peak decreases as the magnetic field gradient increases from 2 % (strongest peak) to 14 % (weakest
peak).

Table II. Summary of acetone gradient NMR data used to determine self-diffusion coefficient.
filename % gradient Calibrated G (T/m) peak area x 108 ln(Am)
spec2 2 0.0101 9.6745 20.69
spec4 4 0.0199 8.0124 20.50
spec6 6 0.0297 5.7537 20.17
spec8 8 0.0394 3.5868 19.70
spec10 10 0.0492 1.9375 19.08
spec12 12 0.0590 0.90954 18.33
spec14 14 0.0687 0.37228 17.43
spec16 16 0.0785 0.129647 16.38
spec18 18 0.0883 0.003975 12.89

The plot of the ln(Am) with respect to G2 according to the rearranged Stejskal-Tanner equation (3)
along with the linear fit to the data is shown in Figure 3. Examination of the data revealed that the
measured peak area for spec18 (see Table II) did not follow the trend of the other spectra and was not
included in any subsequent fits to the data. The remaining data is plotted in Fig. 3 above illustrating the
close agreement to Eq. (2). The fit produced an r2=0.99988 and gave a y0 = 20.79  0.1 and
m = 712.2  0.2. The room temperature self-diffusion coefficient was determined from the fitted slope
as follows:
Slope
D  5.63  0.03 x 10-9 m2s-1 (4)
  (  13  )
2 2

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CHEM 4525 – P-chem lab I Sample lab report

The error in the measured self-diffusion coefficient was determined from the error in the fitted slope. The
viscosity of acetone at 25 °C is estimated using Eq. (2) where the radius of the acetone molecule was
estimated to be 2 Å based on the bond lengths in acetone. The calculated viscosity is
= (0.194  0.001) cP.

21

20
ln(peak area)

19

18

17

16
0.000 0.001 0.002 0.003 0.004 0.005 0.006 0.007
2 2
gradient squared (T /m )

Figure 3. The symbols are the measured ln(Am) values versus magnetic field gradient squared (see Table II). The
line is the result of fitting the data to Eq. 2 (see text for details). Note that spec18 is not plotted in this figure nor
used in the fit.

Discussion
The linear decrease of the logarithm of the peak area with the square of the magnetic field gradient
illustrates the effect of self-diffusion on the NMR spectral signals and confirms the validity of the
Stejskal-Tanner equation. The diffusion coefficient determined from the slope of the plot 5.63  0.03 x
10-9 m2s-1, however, deviates significantly from the published value at 25 °C (D = 4.77 x 10-9 m2 s-1).[4]
No errors were given in reference [4], but from the number of significant digits reported in the paper the
error is most likely on the order of 0.01 x 10-9 m2 s-1. In this work, the error in the measured self-diffusion
coefficient was determined from the error in the fitted slope and therefore does not include any error in
the determined peak areas and/or calibrated field gradients squared. Thus, the reported errors likely
underestimate the true error in the measured diffusion coefficient.
Not surprisingly, the viscosity of acetone determined in this study, = (0.194  0.001) cP, also
differs from the literature value of = 0.307 cP.[4] The discrepancy stems in part from the calculated
self-diffusion coefficient D being 18 % too large. However, the calculated viscosity of acetone is nearly
50% less than the literature value, and therefore cannot be due solely to the error in D. The most severe
error in estimating the viscosity is likely due to the estimate of the molecular radius of acetone. Since the
viscosity calculated from the data is lower than the exact value, it implies that the molecular radius of
acetone was estimated to be too large. Note that if the literature values for the viscosity and self-diffusion
coefficient are used to calculate the effective radius of the acetone molecule, r = 1.49 Å is obtained,
which is relatively close to the estimated value of 2 Å. Another possible source of error may be the
Stokes-Einstein law (2), which is rigorously valid only for spherical objects.

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CHEM 4525 – P-chem lab I Sample lab report

Conclusion
The self-diffusion coefficient and viscosity of acetone were measured using gradient echo NMR
experiment. Stejskal-Tanner equation was used to extract the diffusion constant from the dependence of
the NMR signal intensity on the magnetic field gradient. Einstein-Stokes equation was used to determine
the viscosity. The value of the diffusion constant, D = 5.63  0.03 x 10-9 m2 s-1, is about 18% larger than
the value found in the literature. Using an estimate for the molecular radius of 2 Å, the viscosity of
acetone was calculated to be = (0.194  0.001) cP, which is almost 40% less than the literature value.
The discrepancy in the measured D is due to the errors in the experimental measurements or magnetic
field gradient calibration. The larger error in the calculated viscosity must come from both the error in D
and approximate estimate of the molecular radius for acetone. This experiment demonstrated how NMR
can be used to study the diffusion of molecules and how the diffusion coefficient is related to the viscosity
and the dimensions of the molecule.

References:

1. R. Harris, Nuclear Magnetic Resonance Spectroscopy , John Wiley and Sons Inc., New York, 1987.
2. P. W. Atkins, Physical Chemistry, 3rd edition, W. H. Freeman and Company, New York, 1986.
3. E. O. Stejskal and J. E. Tanner, “Spin diffusion measurements: Spin echoes in the presence of a time-
dependent field gradient,” J. Chem. Phys. 42, 288 (1965).
4. D. W. McCall, D. C. Douglass, and E. W. Anderson, “Diffusion in liquids,” J. Chem. Phys. 31, 1555
(1959).