4.3.1.2.1.

1-1-

4.2.1.2.1.1 M ercury Barometers and U-Tube Manometers

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The word “Barometer” is derived from the Greek word baros "weight" + metron "measure"; the word
was probably coined by Robert Boyle (1627-1691). The principle of the mercury barometer was first
described by Toricelli in 1643; Fortin in 1810 slightly modified the original design. It might seem that
with today’s advances in technology Hg-barometers might be obsolete, so it is interesting to note that
below 300 kPa, the primary pressure standard at NIST is still a mercury manometer, and Hg barometers
and manometers remain the least expensive means to obtain highly accurate absolute pressure
measurements. The absolute pressure is measured by the rise of a mercury column in a capillary, when
one side of it is in contact with a perfect vacuum and the other with the pressure to be determined. There
are a number of effects that need to be considered before the length of the mercury column can be
accurately translated into a pressure (even if expressed as mmHg).

When one immerses a narrow tube in a liquid which wets its surface, the liquid will rise in the tube
(capillary rise, e.g., water, in a glass capillary). On the other hand, if the liquid does not wet the surface
of the capillary, the liquid level will be lowered (capillary depression, e.g., mercury in a glass capillary).
T his difference in liquid level occurs even though there is no external pressure difference across the
liquid column. The height of a
liquid in a capillary is affected
not only by the imposed
pressure differential but also by
the surface tension of the
liquid, and its contact angle,
variables whose sizes determine
the magnitude of the capillary
rise or depression. The surface
tension characterizes the forces
p r e s ent a t the su r fa c e
separating two substances, and
the specific surface energy
measures the change in energy
as a result of a change in
surface area. The surface
tension and energy arise from
the fact that it takes energy to
Figure 4.2.1.2.1.1-1. Capillary depression in a mercury move molecules from the
barometer. For an enlarged image click on the figure. interior of a liquid to its
surface. Hence molecules at the
surface have a higher potential energy.

The top of the liquid in a capillary is generally not horizontally flat, but shows a curvature, either
concave upward, if the liquid wets the surface of the tube material, or convex upward, if the liquid does
 4.3.1.2.1.1-2-

not wet the tube. The curved surface is called the

meniscus (from Greek meniskos "lunar crescent," a
diminutive of mene "moon") and the angle that it
forms with the wall of the tube, the contact angle (see
Fig 4.2.1.2.1.1-1). When the contact angle is less than
90 o the liquid is said to wet the surface; it is called
non-wetting if the contact angle is larger than 90 o. In
Hg manometers, the top of the meniscus is used as the
reference point when the height of the column is
recorded.

When a liquid wets the surface of a capillary, a very

thin film of molecules, which have potential energies
in excess of those in the bulk liquid, is created along
the whole length of the empty tube. The rise of the
liquid will reduce the number of these higher energy
Figure 4.2.1.2.1.1-2. Capillary molecules and hence release energy. T his energy is
depression as a function of capillary used to lift the liquid. A state of balance is attained
radius, surface tension and contact angle. when the change in surface energy as a result of the
For an enlarged image click on the figure. rise of the liquid equals the energy necessary to lift
the liquid. From these considerations one can derive
the height to which a liquid rises in a capillary. The capillary rise is found to depend on the surface
tension, F (dyn/cm 2), and the contact angle, 2, as follows:

C = [2*F*cos(2)]/[D*g*r] cm

where D (g/cm 3) is the density of the manometer liquid, g (cm/s2) the acceleration due to gravity and r
(cm) the inner radius of the capillary. For mercury the surface energy varies with the cleanliness of the
glass surface which it contacts and ranges from about 400 dyn/cm (slightly contaminated) to 500
dyn/cm (exceptionably clean). The contact angle for Hg is on the order of 130 o to 140 o, however, it is
difficult to measure it with a high degree of accuracy. The surface tension and the contact angle
determine the radius (rm) and height (hm) of the meniscus (see Fig. 4.2.1.2.1.1-1); small changes in 2
having a larger effect than variations in F. Using the equation above and the values for the mercury
density and acceleration due to gravity given earlier, the capillary “rise” can be computed for Hg,
which turns out to be negative, because the sign of cos(2). Examples of the capillary depression of Hg
as a function of capillary radius, surface tension and contact angle are shown in Fig 4.2.1.2.1.1-2.

Because of the capillary depression, barometer readings are lower for capillaries than they would be
if infinitely wide tubes were used (see. Fig. 4.2.1.2.1.1-1), hence a correction to the height readings in
capillaries is required. Since the contact angle cannot be determined readily with the desired accuracy,
the meniscus height, which is to a significant degree determined by the contact angle is used instead to
determine the size of the correction factor. The evaluation of the relationship between the meniscus high
and the capillary depression is somewhat complicated and has been reviewed by Gould and Vickers
(1952). These authors give tables, listing the capillary depression correction for Hg at 20 oC as a
function of the size of the capillary bore, the meniscus height and three values of surface tension.
 4.3.1.2.1.1-3-

Two other factors have to be considered in the conversion of the height of the mercury column to a
pressure, i.e., the temperature at which the measurements are taken and the location (latitude and
elevation) at which they are carried out. In correcting the pressures to a given temperature, one has to
take into account, not only the coefficient of thermal expansion of Hg, but also that of the scale on
which the length of the Hg column is determined, because the scale changes its dimensions with
temperature as well. However, it is the difference between the thermal expansion coefficients of the scale
and mercury which determines the size of the correction.

The Handbook of Chemistry and Physics 85 th edition gives a relationship that can be used to reduce the
reading of a mercury barometer with a brass scale to 0/C. The observed height of the mercury column
needs to be reduced by the amount computed from the expression below to find the true pressure in
terms of in mmHg (1mmHg = 133.322 Pa).

)ht = [-0.0001634 h*t]/[1+0.0001818* t],

where h is the observed column height

in mm and t the temperature in Celsius.
This relationship is based on the
thermal expansion coefficient of
181.8A10 -6 /C -1 for mercury and
18.4A10 -6 /C -1 for brass and must be
modified, if measuring scales of other
materials are used.

The latitude and elevation of the

Figure 4.2.1.2.1.1-3. Pressure balance in a U-tube
manometer. For an enlarged image click on the figure.
location of the measurement are
important because the acceleration due
to gravity varies over the Earth’s
surface. The handbook also gives an
expression for the variation of the
acceleration due to gravity as a
function of latitude and height above
the Earth’s surface:

g(2 L,H) = 9.780356 (1 + 0.0052885 sin2 2 L–0.0000059 sin2 2 2 L) –0.003086 H g/(m/s2)

where 2 L is the latitude and H is the height in kilometers. In Table 4.2.1.2.1.1-1 the size of the
correction for some latitudes has been given.

U-tube manometers are often included in low pressure vacuum lines and, if properly calibrated, are quite
useful to determine reaction yields of sample preparation procedures. The manometer (from the Greek
manos meaning sparse, loose, rare and metron "measure") consists of a simple glass capillary U- tube
filled with a working fluid such as mercury. When the pressure in the two arms is identical (e.g., po in
Fig. 4.2.1.2.1.1-3) the mercury level is the same on both sides. If one arm of the tube is evacuated, the
mercury in it will rise until the difference in the level of elevation of the Hg in the two arms equals the
 4.3.1.2.1.1-4-

pressure exerted on the second arm. When the manometer has reached its state of equilibrium, the total
pressure exerted at the bottom of the left arm of the U must equal that at the bottom of the right arm. The
components of these pressures are: the pressure exerted by the capillary depression (pc), the pressure
created by the height of the Hg column (pHg) and the gas pressure, p (see Fig 4.2.1.2.1.1-3). For
equilibrium to exist in the U-tube:

pc1 + pHg1 + p1 = pc2 + pHg2 + p2.

The gas pressure difference between the two sides is given by:

p2 - p1 = (pc1 - pc2 ) + (pHg1 - pHg2)

The pressure generated by a Hg column can be computed from its height as follows:

pHg = F/A = M*g/A = V*D*g/A = (V/A) *D * g = h*D*g

where F is the force, A the area, over which it acts, M the mass of the Hg column, g the acceleration due
to gravity, V the volume of mercury, D its density and h the height of the Hg column. Hence:

p2 - p1 = (pc1 - pc2 ) + D*g*(h’1 - h’2)

From Fig 4.2.1.2.1.1-3 we see that:

h’1 = h1 + h2 + h’2
substituting we find:

p2 - p1 = (pc1 - pc2 ) + D*g*( h1 + h2 )

In case that p1 = 0 (vacuum) and the U-tube is constructed so that the two arms are identical and hence
the two capillary pressures cancel, the relationship simplifies to:

p2 = D*g*( h1 + h2 ).

While a correction for capillary depression is not necessary, the density appropriate for the temperature
at which the manometer is used as well as the acceleration due to gravity applicable for the location
must be substituted.

A finely and accurately scored linear scale is used to determine the difference in Hg height in the two
arms. For the most precise measurements a vernier and a magnifier are arranged to read the scale. The
numerical value for the ( h1 + h2 ) measurement depends on the temperature of the scale and needs to
be corrected for its expansion.

The measurement of the Hg column height has been refined through electrical indicators (Hawkins,
1956) or special lamps with lenses Kobayashi (1980). Meyer and Wade (1962) constructed a
micrometer within a U-tube manometer eliminating sources of error and eye strain. Equipped with a
 4.3.1.2.1.1-5-

system of relays and indicator lights, the device had a range of 0-25 mm, a sensitivity of 0.0025 mm Hg,
and an accuracy of 0.005 mm Hg. Yasumoto, and Nagai (1974) incorporated a reference height Pt
electrode in one arm of the U-tube, the other
contained a depth micrometer for measuring
the variable column length of Hg in the
manometer. The sensitivity achieved by these
authors was about 0.003 mm Hg at 0-800
torr. It is apparent that with such
improvements the manometer can be used to
make highly accurate absolute pressure
determinations, which is one of the reasons
why Hg manometers remain the primary
pressure standard below 300kPa.

The "U"-tube manometer, shown in Fig.

4.2.1.2.1.1-3, has the disadvantage that the
change in height of the liquid in both arms
must be read. This can be avoided by making
the diameter of the volume on one side very
Figure 4.2.1.2.1.1-4. Modified U-tube much larger than the other. In this case the
manometer. For an enlarge image click on the vertical movement on the side with the large
figure. area is much less than that of the side with the
smaller area. The principle is outlined in
Fig.4.2.1.2.1.1-4. Assuming that both the left and right arm of the manometer have cylindrical volumes,
we can compute the rise on the left-hand side (h1) which must occur when the mercury falls in the right
tube to the height h2. This involves the volume V2 on the right and side and volume V1 on the left. The
two volumes must naturally be identical. The cylindrical volumes are:

V 1 = B*(d1/2)2 * h1

V 2 = B*(d2/2)2 * h2
Since
V1 = V2

h1 = h2 * (d2/d1)2

Above we had shown that:

p2 - p1 = (pc1 - pc2 ) + D*g*( h1 + h2 )

substituting for h1 we find:

p2 - p1 = (pc1 - pc2 ) + D*g*h2 *(1 + (d2/d1)2)

For p1 = 0 (vacuum) and assuming that d1 is so large that its capillary depression, pc1, can be neglected
 4.3.1.2.1.1-6-

we can find the pressure p2 as:

p2 = - pc2 + D*g*h2 *(1 + (d2/d1)2)

indicating that for this type of manometer arrangement the capillary depression correction needs to be
considered.

Table 4.2.1.2.1.1-1 Latitude correction for Hg barometers

Observed Pressure in mmHg

Latitude
740
(degrees) 760 780

25 65 1.27 1.30 1.33

30 60 0.98 1.01 1.04

35 55 0.67 0.69 0.71

40 50 0.34 0.35 0.36

For latitudes less than 45 o the correction should be subtracted from the observed height; for
latitudes greater than 45 o the correction should be added.