Fall 2014

MECH 121

R.A. Marks

MECH 121: HOMEWORK #2

DUE: Wednesday, October 8, 2014

I. e critical temperature and pressure for O2 are 154.59K and 5.043 MPa, respectively.
(a) Determine the constants a and b that should be used in van der Waals equation of state to
ensure agreement with the critical temperature and pressure.
(b) e critical molar volume of O2 is 73 cm3/mol. How well does this agree with the critical
value predicted by van der Waals equation when the values of a and b determined above are
used?
(c) Produce a P vs. v graph containing isotherms for O2 (assuming van der Waals equation of
state) at 135K, 154.59K, 250K, and 400K. On the same graph, plot isotherms at the same
temperatures for the ideal gas law. Comment on the agreement/disagreement between the
two sets of curves. (NOTE: van der Waals equation is not continuous at v = b . It is not
necessary, nor does it really make sense, to plot your isotherms for v b . Additionally, you
may wish to display the v axis on a logarithmic scale to make the inflections in the curves at
and below the critical temperature more apparent.)
II. Water at 20C and 101.325 kPa has a density of 998.2063 kg/m 3 . Under these conditions, the
volumetric expansivity, , and isothermal compressibility, T , are 0.206 103 K 1 and
4.591 104 MPa 1 , respectively. In this problem, we will explore the suitability of van der Waals
equation of state and v = v0 exp [ (T T0 ) T (P P0 )] , which was derived in class under the
assumptions that and T are constants.
(a) Either look up the van der Waals constants for water, or compute them using the critical
temperature and pressure. en use van der Waals law to determine the specific volume of
water at 20C and 101.325 kPa. (You will need to find the roots to a cubic polynomial in v.)
How does your result compare to the known specific volume (reciprocal of density given
above)?
(b) By using the cyclic rule and reciprocal rule for partial derivatives, develop expressions for T
and for a van der Waals substance. Next evaluate your expressions for T and at 20C,
101.325 kPa, and the volume found in part (a). How do the results compare to the known
values given above?
(c) Now determine the percent error that results from using v = v0 exp [ (T T0 ) T (P P0 )]
to compute the specific volume of water at 20C and 50,000 kPa. To find the percent error,
you should compare relative to the actual value in the compressed liquid tables at 50,000 kPa
and 20C.

Fall 2014

MECH 121

R.A. Marks

(d) You should have found that the specific volume predicted by the equation is slightly smaller
than the volume listed in the table. Why do you suppose the predicted value is smaller
instead of larger than the actual value?
(e) Now compute the specific volume at 100C and 101.325 kPa using
v = v0 exp [ (T T0 ) T (P P0 )] . Your result should again be somewhat underestimated,
but by more than in part (c). What can you conclude about the temperature dependence of
from this result? In other words, does it appear increases or decreases with increasing
temperature?
(f ) Now compute the specific volume at 380C and 50,000 kPa using
v = v0 exp [ (T T0 ) T (P P0 )] and compare to the tabulated value. What is the percent
error? Do you expect this results more from the assumption made about or T ?