Lectures on Heat (1)


Heat
Feeling and seeing temperature changes
Within some reasonable temperature range, we can get a rough idea how warm something is by touching it. But this can be unreliable—if you put one hand in cold water, one in hot, then plunge both of them into lukewarm water, one hand will tell you it’s hot, the other will feel cold. For something too hot to touch, we can often get an impression of how hot it is by approaching and sensing the radiant heat. If the temperature increases enough, it begins to glow and we can see it’s hot!
The problem with these subjective perceptions of heat is that they may not be the same for everybody. If our two hands can’t agree on whether water is warm or cold, how likely is it that a group of people can set a uniform standard? We need to construct a device of some kind that responds to temperature in a simple, measurable way—we need a thermometer.
The first step on the road to a thermometer was taken by one Philo of Byzantium, an engineer, in the second century BC. He took a hollow lead sphere connected with a tight seal to one end of a pipe, the other end of the pipe being under water in another vessel.

 




To quote Philo: “…if you expose the sphere to the sun, part of the air enclosed in the tube will pass out when the sphere becomes hot. This will be evident because the air will descend from the tube into the water, agitating it and producing a succession of bubbles.
Now if the sphere is put back in the shade, that is, where the sun’s rays do not reach it, the water will rise and pass through the tube …”
“No matter how many times you repeat the operation, the same thing will happen.
In fact, if you heat the sphere with fire, or even if you pour hot water over it, the result will be the same.”
Notice that Philo did what a real investigative scientist should do—he checked that the experiment was reproducible, and he established that the air’s expansion was in response to heat being applied to the sphere, and was independent of the source of the heat.

Classic Dramatic Uses of Temperature-Dependent Effects

This expansion of air on heating became widely known in classical times, and was used in various dramatic devices. For example, Hero of Alexandria describes a small temple where a fire on the altar causes the doors to open
The altar is a large airtight box, with a pipe leading from it to another enclosed container filled with water. When the fire is set on top of the altar, the air in the box heats up and expands into a second container which is filled with water. This water is forced out through an overflow pipe into a bucket hung on a rope attached to the door hinges in such a way that as the bucket fills with water, it drops, turns the hinges, and opens the doors. The pipe into this bucket reaches almost to the bottom, so that when the altar fire goes out, the water is sucked back and the doors close again. (Presumably, once the fire is burning, the god behind the doors is ready to do business and the doors open…)
Still, none of these ingenious devices is a thermometer. There was no attempt (at least none recorded) by Philo or his followers to make a quantitative measurement of how hot or cold the sphere was. And the “meter” in thermometer means measurement
The First Thermometer
Galileo claimed to have invented the first thermometer. Well, actually, he called it a thermoscope, but he did try to measure “degrees of heat and cold” according to a colleague, and that qualifies it as a thermometer. (Technically, a thermoscope is a device making it possible to see a temperature change, a thermometer can measure the temperature change.) Galileo used an inverted narrow-necked bulb with a tubular neck, like a hen’s egg with a long glass tube attached at the tip.




He first heated the bulb with his hands then immediately put it into water. He recorded that the water rose in the bulb the height of “one palm”. Later, either Galileo or his colleague Santorio Santorio put a paper scale next to the tube to read off changes in the water level. This definitely made it a thermometer, but who thought of it first isn’t clear (they argued about it). And, in fact, this thermometer had problems.
Question: what problems? If you occasionally top up the water, why shouldn’t this thermometer be good for recording daily changes in temperature?
Answer: because it’s also a barometer! But—Galileo didn’t know about the atmospheric pressure.
Torricelli, one of Galileo’s pupils, was the first to realize, shortly after Galileo died, that the real driving force in suction was external atmospheric pressure, a satisfying mechanical explanation in contrast to the philosophical “nature abhors a vacuum”. In the 1640’s, Pascal pointed out that the variability of atmospheric pressure rendered the air thermometer untrustworthy.
Liquid-in-glass thermometers were used from the 1630’s, and they were of course insensitive to barometric pressure. Meteorological records were kept from this time, but there was no real uniformity of temperature measurement until Fahrenheit, almost a hundred years later.

Newton’s Anonymous Table of Temperatures
The first systematic account of a range of different temperatures, “Degrees of Heat”, was written by Newton, but published anonymously, in 1701. Presumably he felt that this project lacked the timeless significance of some of his other achievements.
Taking the freezing point of water as zero, Newton found the temperature of boiling water to be almost three times that of the human body, melting lead eight times as great (actually 327C, whereas 8x37=296, so this is pretty good!) but for higher temperatures, such as that of a wood fire, he underestimated considerably. He used a linseed oil liquid in glass thermometer up to the melting point of tin (232°C). (Linseed oil doesn’t boil until 343°C, but that is also its autoignition temperature!)
Newton tried to estimate the higher temperatures indirectly. He heated up a piece of iron in a fire, then let it cool in a steady breeze. He found that, at least at the lower temperatures where he could cross check with his thermometer, the temperature dropped in a geometric progression, that is, if it took five minutes to drop from 80° above air temperature to 40° above air temperature, it took another five minutes to drop to 20° above air, another five to drop to 10° above, and so on. He then assumed this same pattern of temperature drop was true at the high temperatures beyond the reach of his thermometer, and so estimated the temperature of the fire and of iron glowing red hot. This wasn’t very accurate—he (under)estimated the temperature of the fire to be about 600°C.
Fahrenheit’s Excellent Thermometer
The first really good thermometer, using mercury expanding from a bulb into a capillary tube, was made by Fahrenheit in the early 1720’s. He got the idea of using mercury from a colleague’s comment that one should correct a barometer reading to allow for the variation of the density of mercury with temperature. The point that has to be borne in mind in constructing thermometers, and defining temperature scales, is that not all liquids expand at uniform rates on heating—water, for example, at first contracts on heating from its freezing point, then begins to expand at around forty degrees Fahrenheit, so a water thermometer wouldn’t be very helpful on a cold day. It is also not easy to manufacture a uniform cross section capillary tube, but Fahrenheit managed to do it, and demonstrated his success by showing his thermometers agreed with each other over a whole range of temperatures. Fortunately, it turns out that mercury is well behaved in that the temperature scale defined by taking its expansion to be uniform coincides very closely with the true temperature scale, as we shall see later.
Amontons’ Air Thermometer: Pressure Increases Linearly with Temperature
A little earlier (1702) Amontons introduced an air pressure thermometer. He established that if air at atmospheric pressure (he states 30 inches of mercury) at the freezing point of water is enclosed then heated to the boiling point of water, but meanwhile kept at constant volume by increasing the pressure on it, the pressure goes up by about 10 inches of mercury. He also discovered that if he compressed the air in the first place, so that it was at a pressure of sixty inches of mercury at the temperature of melting ice, then if he raised its temperature to that of boiling water, at the same time adding mercury to the column to keep the volume of air constant, the pressure increased by 20 inches of mercury. In other words, he found that for a fixed amount of air kept in a container at constant volume, the pressure increased with temperature by about 33% from freezing to boiling, that percentage being independent of the initial pressure.


Definitions of Words and Terms Used in the Gas Processing Industry

absorber
A tower or column that provides contact between natural gas being processed and a liquid solvent.
absorption
The operation in which one or more components in the gas phase are transferred to (absorbed into) a liquid solvent.
absorption factor
A factor which is an indication of the tendency for a given gas phase component to be transferred to the liquid solvent. It is generally expressed as A = L/KV where L and V are the molar flows of liquid and vapor, and K is the average value of the vapor-liquid equilibrium constant for the component of concern.
absorption oil
A hydrocarbon liquid used to absorb and recover components from the natural gas being processed.
acid gas
The hydrogen sulfide and/or carbon dioxide contained in, or extracted from, gas or other streams.
adiabatic expansion
The expansion of a gas, vapor, or liquid stream from a higher pressure to a lower pressure in which there is no heat transfer between the gas, vapor, or liquid and the surroundings.
adsorbent
A solid substance used to remove components from natural gas being processed.
adsorption
The process by which gaseous components are adsorbed on solids because of their  molecular attraction to the solid surface.
amine (alkanolamine)
Any of several liquid compounds containing amino nitrogen generally used in water solution to remove, by reversible chemical reaction, hydrogen sulfide and/or carbon dioxide from gas and liquid hydrocarbon streams.
API Gravity
An arbitrary scale expressing the relative density of liquid petroleum products. The scale is calibrated in degrees API, calculated by the following formula:
γ = relative density
associated gas
Gaseous hydrocarbons occuring as a free-gas phase under original oil-reservoir conditions of temperature and pressure.
atmospheric pressure
The pressure exerted on the earth by the earth’s atmosphere. A pressure of 760 mm of mercury, 29.92 inches of mercury, or 14.696 psia is used as a standard for some measurements. State regulatory bodies have set other standards for use in
measuring the legal volume of gas. Atmospheric pressure may also refer to the absolute ambient pressure at any given location.
barrel
A common English-unit mesure of liquid volume which, in the petroleum industry, equals 42 U.S. liquid gallons for petroleum or natural gas liquid products measured at 60°F and equilibrium vapor pressure. One barrel equals 0.159 cubic meters, or 6.29 barrels per cubic meter .
blanket gas
A gas phase maintained in a vessel containing liquid to protect the liquid against air contamination, to reduce the hazard of explosion, or to maintain pressure of the liquid. The source of the gas is external to the vessel.
blow case
A small vessel in which liquid is accumulated and then forced from the vessel by applying gas or air pressure above the liquid level.
blowdown
The act of emptying or depressuring a vessel. This may also refer to discarded material,  such as blowdown water from a boiler or cooling tower.
boilaway test
Sometimes used to describe the GPA weathering test for LPgas. Refer to definition for "weathering test".
bottoms
The liquid or residual matter which is withdrawn from the bottom of a fractionator or other vessel during processing or while in storage.
B-P mix
A liquefied hydrocarbon product composed chiefly of butanes and propane. If it originates in a refinery, it may also contain butylenes and propylene. More specifically, it conforms to the GPA specifications for commercial B-P mixes as described in GPA Standard 2140.
breathing
The movement of vapor in or out of an atmospheric pressure storage tank because of a change of level of the stored liquid, a change in the temperature of the vapor space above the liquid, or a change of atmospheric pressure.
bs&w (basic sediment and water)
Waste that collects in the bottom of vessels and tanks containing petroleum or petroleum products.
bubble point
The temperature at a specified pressure at which the first stable  vapor forms above a liquid.
butane, commercial
A liquefied hydrocarbon consisting predominately of butane and/or butylene and which conforms to the GPA specification for commercial butane defined in GPA Standard 2140.
butane, normal
In commercial transactions, a product meeting the GPA specifications for commercial butane and, in addition, containing a minimum of 95 liquid volume percent normal butane. Chemically, normal butane is an aliphatic compound of the paraffin series having the chemical formula C4H10 and having all of its carbon atoms joined in a straight chain.
calorimeter
An apparatus which is used to determine the heating value of a combustible material.
carbonyl sulfide
A chemical compound of the aldehyde group containing a carbonyl group and sulfur (COS). Sometimes a contaminant in natural gas and NGL. It may need to be removed in order to meet sulfur specifications.
casinghead gas
Unprocessed natural gas produced from a reservoir containing oil. It contains heavier hydrocarbon vapors and is usually produced under low pressure from a casing head on the well.
charcoal test
A test standardized by the Gas Processors Association and the American Gas Association for determining the natural gasoline content of a given natural gas. The gasoline is adsorbed from the gas on activated charcoal and then recovered by distillation.
The test is prescribed in Testing Code 101-43, a joint publication of AGA and GPA.
chromatography
A technique for separating a mixture into individual components by repeated adsorption and desorption on a confined solid bed. It is used for analysis of natural gas and NGL.
Claus Process
A process to convert hydrogen sulfide into elemental sulfur by selective oxidation.
compressibility factor
A factor, usually expressed as "Z," which gives the ratio of the actual volume of gas at a given temperature and pressure to the volume of gas when calculated by the ideal gas law.
compression ratio
The ratio of the absolute discharge pressure from a compressor to the absolute intake pressure. Also applies to one cylinder of a reciprocating compressor and one or more stages of a rotating compressor.
condensate
The liquid formed by the condensation of a vapor or gas; specifically, the hydrocarbon liquid separated from natural gas because of changes in temperature and pressure when the gas
from the reservoir was delivered to the surface separators. In a steam system it may be water that is condensed and returned to the boilers.
convergence pressure
The pressure at a given temperature for a hydrocarbon system of fixed composition at which the vapor-liquid equilibrium Kvalues of the various components in the system become, or
tend to become, unity. The convergence pressure is used to adjust vapor-liquid equilibrium K-values to the particular system under consideration. (See TP-22)
copper strip test
A test using a small strip of pure copper to determine qualitatively the hydrogen sulfide corrosivity of a product. Refer to GPA LP-gas copper strip test (Copper Strip Method), ASTM D-1838 test procedure.
cricondenbar
The highest pressure at which liquid and vapor phases can exist at equilibrium in a  multicomponent system.
cricondentherm
The highest temperature at which liquid and vapor phases can exist at equilibrium in a multicomponent system.
critical density
The density of a substance at its critical temperature and critical pressure.
critical pressure
The vapor pressure of a substance at its critical temperature. critical temperature
For a pure component, the maximum temperature at which the component can exist as a liquid.
cryogenic plant
A gas processing plant which is capable of producing natural gas liquid products, including ethane, at very low operating temperatures, usually below minus 50°F.
cubic meter
A unit of volume measurement commonly used in international commerce for petroleum, petroleum products and natural gas. One cubic meter measured at 60°F = 264.172 U.S.
gallons = 6.29 barrels = 35.315 cubic feet measured at 60°F.
deaerator
An item of equipment used for removing air or other non-condensible gases from a process stream or from steam condensate or boiler feed water.
debutanizer
A fractionator designed to separate butane (and more volatile
components if present) from a hydrocarbon mixture.
dehydration
The act or process of removing water from gases or liquids.
demethanized product
A product from which essentially all methane and lighter materials
have been removed.
demethanizer
A fractionator designed to separate methane (and more volatile
components if present) from a hydrocarbon mixture.
depropanizer
A fractionator designed to separate propane (and more volatile
components if present) from a hydrocarbon mixture.
desiccant
A substance used in a dehydrator to remove water and moisture.
Also a material used to remove moisture from the air.
desulfurization
A process by which sulfur and sulfur compounds are removed
from gases or liquid hydrocarbon mixtures.
dew point
The temperature at any given pressure, or the pressure at any
given temperature, at which liquid initially condenses from a
gas or vapor. It is specifically applied to the temperature at
which water vapor starts to condense from a gas mixture
(water dew point), or at which hydrocarbons start to condense
(hydrocarbon dew point).
distillation
The process of separating materials by successively heating to
vaporize a portion and then cooling to liquefy a part of the
vapor. Materials to be separated must differ in boiling point
and/or relative volatility..
doctor test
A qualitative method for detecting hydrogen sulfide and mercaptans
in NGL. The test distinguishes between "sour" and
"sweet" products.
dry gas
(1) Gas whose water content has been reduced by a dehydration
process. (2) Gas containing little or no hydrocarbons commercially
recoverable as liquid product. Gas in this second
definition preferably should be called lean gas.
end point
The maximum temperature observed on the thermometer
during an ASTM distillation test.
EP-mix (ethane-propane mix)
A product consisting of a mixture of essentially ethane and
propane.
expansion turbine
A device which converts part of the energy content of a gas or
liquid stream into mechanical work by expanding the gas or
liquid through a turbine from which work is extracted.
extraction
The process of transferring one or more components from one
liquid phase to another by virtue of different solubility in the
two liquids. It is also used to indicate removal of one or more
constituents from a stream.
field separator
A vessel in the oil or gas field for separating gas, hydrocarbon
liquid, and water from each other.
flash point
The lowest temperature at which vapors from a hydrocarbon
liquid will ignite. See ASTM D-56.
fractionation
See definition of "distillation." Generally used to describe
separation of a mixture of hydrocarbons into individual products
based on difference in boiling point and/or relative volatility.
freeze valve
A specially constructed and calibrated valve designed and
used solely for determining the water content in propane product.
See ASTM D-2713.
gas constant (R)
The constant multiplier in the Ideal Gas Law. Numerically,
R=PV/T, if V is the volume of one mole of an ideal gas at temperature
T and pressure P.
gas hydrate
Refer to definition of "hydrate".
gas injection
The injection of natural gas into a reservoir to maintain or
increase the reservoir pressure or reduce the rate of decline of
the reservoir pressure.
gas lift
A method for bringing crude oil or water to the surface by
injecting gas into the producing well bore.
gas-oil ratio (GOR)
The ratio of gas to liquid hydrocarbon produced from a well.
This may be expressed as standard cubic feet of gas per barrel
of stock tank liquid.
gas processing
The separation of constituents from natural gas for the purpose
of making salable products and also for treating the residue
gas to meet required specifications.
gas processing plant
A plant which processes natural gas for recovery of natural
gas liquids and sometimes other substances such as sulfur.
gas-well gas
The gas produced or separated at surface conditions from the
full well stream produced from a gas reservoir.
gas-well liquids
The liquid separated at surface conditions from the full well
stream produced from a gas reservoir.
gathering system
The network of pipelines which carry gas from the wells to the
processing plant or other separation equipment.
gpm/GPM
(1) gpm (gallons per minute): The term used to describe the
rate of flowing fluid in gallons per minute. (2) GPM — Preferably
Gal/Mcf (gallons per thousand cubic feet): This term refers
to the content in natural gas of components which are
recoverable or recovered as liquid products.
heat medium (heating medium)
A material, whether flowing or static, used to transport heat
from a primary source such as combustion of fuel to another
material. Heating oil, steam, and an eutectic salt mixture are
examples of heat mediums.
heating value (heat of combustion)
The amount of heat obtained by the complete combustion of a
unit quantity of material. The gross, or higher, heating value
is the amount of heat obtained when the water produced in
the combustion is condensed. The net, or lower, heating value
is the amount of heat obtained when the water produced in
the combustion is not condensed.
heavy ends
The portion of a hydrocarbon mixture having the highest boiling
point. Usually hexanes or heptanes and all heavier hydrocarbons
are the heavy ends in a natural gas stream.
hexanes plus (or heptanes plus)
The portion of a hydrocarbon fluid mixture or the last component
of a hydrocarbon analysis which contains the hexanes (or
heptanes) and all hydrocarbons heavier than the hexanes (or
heptanes).
hydrate
A solid material resulting from the combination of a hydrocarbon
with water under pressure.
immiscible
Liquids that will not mix nor blend to give homogeneity are
said to be immiscible.
ideal gas (also called "perfect" gas)
A gas that obeys the ideal gas law expressed as PV=RT, see
Fig. 1-4.
inerts
Elements or compounds not acted upon chemically by the surrounding
environment. Nitrogen and helium are examples of
inert constituents of natural gases.
isobutane
In commercial transactions, a product meeting the GPA specification
for commercial butane and, in addition, containing a
minimum of 95 liquid volume percent isobutane. Chemically,
a hydrocarbon of the paraffin series with the formula C4H10
and having its carbon atoms branched.
jacket water
Water which fills, or is circulated through, a casing which partially
or wholly surrounds a vessel or machine element in order
to remove, add, or distribute heat in order to control the temperature
within the vessel or element.
Joule-Thomson effect
The change in gas temperature which occurs when the gas is
expanded at constant enthalpy from a higher pressure to a
lower pressure. The effect for most gases at normal pressure,
except hydrogen and helium, is a cooling of the gas.
lead acetate test
A method for detecting the presence of hydrogen sulfide by
discoloration of paper which has been moistened with lead acetate
solution. See ASTM D-2420.
lean gas
(1) The residue gas remaining after recovery of natural gas
liquids in a gas processing plant. (2) Unprocessed gas containing
little or no recoverable natural gas liquids.
lean oil
Absorption oil as purchased or recovered by the plant, or oil
from which the absorbed constituents have been removed.
lift gas
Gas used in a gas lift operation.
light ends
The low-boiling, easily evaporated components of a hydrocarbon
liquid mixture.
light hydrocarbons
The low molecular weight hydrocarbons such as methane, ethane,
propane and butanes.
LNG (liquefied natural gas)
The light hydrocarbon portion of natural gas, predominately
methane, which has been liquefied.
loading rack
A structural and piping installation alongside a railroad track
or roadway used for the purpose of filling railroad tank cars
or transport trucks.
LPG (liquefied petroleum gas)
Refer to definition of "LP-gas".
LP-gas (liquefied petroleum gas)
Predominately propane or butane, either separately or in mixtures, which is maintained in a liquid state under pressure within the confining vessel.
LRG (liquefied refinery gas)
Liquid propane or butane produced by a crude oil refinery. It may differ from LP-gas in that propylene and butylene may be present.
LTX (low temperature extraction unit)
A unit which uses the cooling of a constant enthalpy expansion to increase liquid recovery from streams produced from high pressure gas condensate reservoirs. Also called LTS (low temperature separation) unit.
Mcf
An abbreviation for one thousand cubic feet of gas.
MMcf
An abbreviation for one million cubic feet of gas.
mercaptan
Any of a homologous series of compounds of the general formula RSH. All mercaptans possess a foul odor.
miscible flood
A method of secondary recovery of fluids from a reservoir by
injection of fluids that are miscible with the reservoir fluids.