In this paper we compare the amounts of ethanol in breath and in blood afte
r ingestion of whisky using analysis by selected ion flow tube mass spectro
metry (SIFT-MS). Blood ethanol concentrations were also obtained using stan
dard hospital forensic procedures for blood alcohol analyses. We demonstrat
e the quantitative nature of SIFT-MS analysis by correlating the observed a
lcohol content of the headspace above 5-mL amounts of venous blood and aque
ous solution to which known trace amounts of alcohol have been added. This
procedure provides a Henry's Law coefficient for ethanol in aqueous solutio
n at 298 +/-t 3 K of 209 +/- 7 mol/kg*bar. We also demonstrate that measure
ment of the ethanol concentration in the alveolar portion of a single breat
h using the SIFT-MS technique gives an accurate measure of blood alcohol an
d could obviate the need for blood samples in forensic processing. The stor
age performance of breath samples in Mylar bags with a volume greater than
1 L has been shown to maintain the mixture integrity for ethanol but not fo
r some other species. Copyright (C) 2001 John Wiley & Sons, Ltd.