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thermodynamics C explain the physical basis of heat and temperature, and the
effects of heat on solids, liquids, gases and solutions
David Williams
C explain the mechanisms of heat transfer in relation to the cause
and prevention of perioperative heat loss from a patient
C describe different methods of temperature measurement, and
explain how they work
Abstract
Many items of equipment used in anaesthesia and intensive care rely on the
principles of thermodynamics for their operation. Heat loss from the human
First law: (‘Conservation of energy’): energy can be transformed,
body may result in perioperative hypothermia and increased morbidity. It is
but cannot be created or destroyed.
therefore essential to have a sound understanding of the underlying phys-
ical principles. This article outlines thermodynamic concepts which are rele-
Second law: entropy (the state of molecular disorder) always
vant to clinical practice and includes: heat capacity and latent heat; thermal
increases or remains constanta e that is, energy always moves
effects on solids, liquids, gases and solutions; mechanisms of heat transfer;
from a higher to lower state (hot to cold), but never in the reverse
and techniques of temperature measurement.
direction unless work is done.
a
David Williams FRCA DipDHM is a Consultant Anaesthetist at the Welsh “It’s the Second Law of Thermodynamics: Sooner or later everything
Centre for Burns, Swansea, UK. Conflicts of interest: none declared. turns to s**t!” e Woody Allen, Husbands and Wives (1992).
ANAESTHESIA AND INTENSIVE CARE MEDICINE 13:3 111 Ó 2012 Elsevier Ltd. All rights reserved.
PHYSICS
100 divisions
180 divisions
(Highlights indicate fixed points used for calibration)
Conversion: NB
1
C = K – 273.15 The SI unit for temperature is ‘Kelvin’, not ‘degrees Kelvin’
2
F = (C x 9/5) + 32 ‘Centigrade’ means any scale divided into 100 divisions.
Temperature intervals: 1K = 1C = 1.8F The correct term is ‘degrees Celsius’.
Figure 1
a mass (m) of substance undergoing a temperature change (DT ): phase without a change in temperature; and represents the latent
Q ¼ m$c$DT. (i.e. hidden) energy that is required to break bonds, or is released
The specific latent heat (l ) (J/kg) is the amount of energy by formation of new bonds. The value of l depends on the
added or released as heat when a unit mass of substance changes substance and the phase transition (Figures 2a,b). Q ¼ m$l.
a. Phases and transitions b. A graph of temperature against energy added when 1 g of ice
at –30oC is converted to steam at 120oC
Plasma
120 e
d
Deionization
100
Ionization
IE
Temperature (C)
Steam
c
Water + steam
Gas
Lv b
Va
0 a
po
Co
Water
riz
Ice
nd
Ice
at
en
io
+ water
sa
Deposition
n
Sublimation
tio
–30
n
Energy added:
el
n
M
a = m . cice . ΔT
sio
= 63
Fu
Lf b = m . lf water = 333
Solid c = m . cwater . ΔT = 419
d = m . lv water = 2260
Lf,v,s = latent heat of fusion, vaporization, sublimation e = m . csteam . ΔT = 40
IE = ionization enthalpy Total = 3115
Figure 2
ANAESTHESIA AND INTENSIVE CARE MEDICINE 13:3 112 Ó 2012 Elsevier Ltd. All rights reserved.
PHYSICS
If c and l are not defined in terms of mass, they are called bonds (freezing). This has the effect of raising the boiling point
‘heat capacity’ (C) (J/K) and ‘latent heat’ (L) (J). Defining them and lowering the freezing point, and depends on the mass of the
in terms of standard mass (i.e. ‘specific’) allows the properties of impurities present (‘colligative properties’), rather than their
different substances to be compared. chemical properties.
As a liquid evaporates, latent heat of vaporization is drawn Thermodynamic processes may be described as adiabatic (or
from the remaining liquid and surroundings. Hence for an isocaloric) (no heat transfer to or from the surrounding environ-
anaesthetic vaporizer, the temperature and saturated vapour ment); isothermal (constant temperature); isobaric (constant
pressure of the volatile agent will fall during use, resulting in pressure); or isochoric (constant volume). The internal energy of
a decrease in delivered vapour concentration. Vaporizer design a system is the sum of its molecular KE (due to molecular trans-
therefore includes thermostabilization e high-conductivity lation, rotation, and vibration) and potential energy (due to inter-
materials (e.g. steel, copper) to conduct heat from the molecular bonds). If work is performed to compress a gas, the
surroundings to the vapourizing chamber, and a large mass (e.g. internal energy and therefore the temperature of the gas will
metal, water) to act as a heat reservoir; and thermocompensa- increase. Rapid compression will not allow sufficient time for heat
tion e for example a temperature-controlled variable bypass to be transferred from the gas to the surrounding environment
valve incorporating a bimetallic strip. (adiabatic change), resulting in a sudden increase in temperature of
Increasing temperature tends to decrease the viscosity (h) of the gas: however slow compression will allow time for the heat to be
liquids; increase the viscosity of gases; and decrease the density lost to the surroundings (isothermal change) and no increase in gas
(r) of both. Most aqueous solutions undergo an endothermic temperature will occur. If the valve of an oxygen cylinder is opened
reaction (i.e. absorb energy) as they are formed. With increasing suddenly, the rapid increase in pressure at a valve downstream may
temperature, the solubility of a solid in a liquid generally result in adiabatic heating and potential ignition of any flammable
increases up to a limit (saturation); however the solubility of contaminants (e.g. mineral oil) if present. Cylinder valves should
a gas decreases in an aqueous solvent, but increases in an therefore be opened slowly to allow isothermal change to occur.
organic solvent. Dissolved impurities obstruct molecules of Conversely, rapid expansion of a gas without the addition of heat
liquid from leaving the liquid phase (evaporation) or forming energy from the environment (adiabatic change) will cause
Conduction When objects are in physical The metal case of the stove C Cold intravenous fluids C Fluid warmer
contact, direct exchange of gets hot. C Irrigation fluid C Warmed irrigation fluids
KE between adjacent C Conduction to operating C Foam mattress
vibrating atoms or table C Heated mattress
molecules occurs.
Convection Bulk flow and diffusion of Air above the stove and C Air movement in theatre C Forced convection
fluids (liquids or gases). water in the kettle get hot. C Laminar air flow cabinet warming devices
Warm fluids decrease in (e.g. Bair HuggerÒ)
density and rise, causing C Blankets/drapes
movement of high-energy
molecules.
Radiation Electromagnetic radiation You feel heat on your skin at C Exposed skin C Radiant heaters
(e.g. infrared, microwaves). a distance from the fire. C Blankets/drapes
Does not require a medium C Metallized polyester
for propagation e heat from ‘space blanket’ in post-
the sun reaches us across operative care unit
the vacuum of space.
Phase change Release or uptake of latent If steam from the kettle hits Latent heat of evaporation C Heat and moisture
heat of fusion or your skin and condenses to from: exchanger (HME)
vaporization when bonds water, you get scalded by C surgical wounds C Circle breathing system
are made or broken. the heat that is released. C skin prep C Breathing system
C burns humidifier
C respiratory tract (esp. if
cold dry gas from
anaesthetic machine)
Table 1
ANAESTHESIA AND INTENSIVE CARE MEDICINE 13:3 113 Ó 2012 Elsevier Ltd. All rights reserved.
PHYSICS
a reduction in internal energy, resulting in cooling (the Joulee temperature (Tamb); i.e. dQ/dt ¼ h (TtTamb), where (h) is the
Thomson effect). This is employed in the design of a cryoprobe. heat transfer coefficient (W m2 K). The temperature of an object
which has cooled from initial temperature (T0) over a time period
Heat transfer (t) is therefore given by: Tt ¼ Tamb þ (T0 Tamb) e$ht
Thermal transfer can occur by conduction, convection, radia- Electromagnetic radiation of an appropriate wavelength may
tion and phase-change transfer (Table 1). These processes are transfer its energy to the electrons which surround an atom and
responsible for approximately 5%, 30%, 40% and 25% of peri- cause them to move from low to high energy levels, increasing
operative heat loss respectively. the kinetic energy of the substance (absorption). The reverse
process may also occur so that heat energy in a substance is
Thermal conductivity (k) (W/m/K) describes the ability of converted to electromagnetic wave energy of a specific wave-
a material to transfer heat by conduction. The value of k depends length (emission). Reflection is simply absorption followed by
on the substance and phase; and also increases with average emission. If the wavelength of the incident radiation does not
temperature. High k substances transfer energy rapidly and may correspond to the resonant frequency of the electrons, the waves
be used in heat sinks to conduct heat away from a site to the pass through the substance (transmission).
surrounding environment: low k substances are used as thermal Materials emit and absorb radiation equally effectively e
insulation. Gases (except for those with low density such as otherwise the second law of thermodynamics would be violated.
hydrogen and helium) generally have low k and are therefore Infrared (thermal) radiation (wavelength 0.7e300 mm) is best
good insulators, provided that they are not moving and causing emitted and absorbed by matt black rough surfaces, and best
convective loss. Materials incorporating air-filled pockets (e.g. reflected by shiny white smooth surfaces. A black body is an
bubble wrap, foam rubber) are therefore effective insulators idealized object which is a perfect absorber and emitter of
against heat loss by conduction. For a conducting substance of thermal radiation. The rate of heat transfer by radiation is
area (A), thickness (x) and temperature difference (DT ), the rate proportional to the fourth power of the temperature difference
of heat transfer (dQ/dt) ¼ k$A$DT/x. (StefaneBoltzmann law).
The rate of heat transfer by convection may be predicted by Dewar (“ThermosÒ”) flasks maintain the temperature of
Newton’s law of cooling, which states that the rate of change of their contents by using a combination of silvered walls to
temperature of an object (dT/dt) is proportional to the difference reduce radiation, and a vacuum to reduce conduction and
between its own instantaneous temperature (Tt) and the ambient convection.
Thermal expansion
C Solid Metal strip thermometer, bimetallic strip
C Liquid Glass bulb thermometer (e.g. mercury, alcohol)
Galilean thermometer (density change of water)
C Gas Dial thermometer (e.g. Bourdon gauge)
Chemical Liquid crystal thermometer: pitch of spiral chiral nematic liquid crystal
changes with temperature, reflecting different wavelengths (colours) of light.
Electrical
C Resistance (R) Resistance temperature device (RTD). Resistance wire (e.g. Pt) in a
Wheatstone bridge. Approx. linear [R with [temperature.
Thermistor (metal oxide semiconductor). May be manufactured with
negative or positive temperature coefficient; i.e. non-linear [ or YR
with [temperature.
C Voltage difference Integrated circuit semiconductor temperature sensor e voltage
difference between junctions of two transistors changes with temperature.
C Thermoelectric Thermocouple e.m.f. is generated by electron flow when a temperature
(PeltiereSeebeckeThomson) effect difference occurs at the junctions of two dissimilar metals, e.g
Cu/CueNi (‘constantan’) or PteRh.
Approx. linear [ in e.m.f. with [temperature.
C Crystal resonance Vibrating quartz crystal: resonant frequency [ w1 KHz/ C
Infrared radiation Tympanic thermometer, Pyrometer.
Output proportional to incident radiation. Sensing elements include:
Photon detector, pyroelectric (charge), thermopile (multiple thermocouples),
bolometer (resistance).
Table 2
ANAESTHESIA AND INTENSIVE CARE MEDICINE 13:3 114 Ó 2012 Elsevier Ltd. All rights reserved.
PHYSICS
ANAESTHESIA AND INTENSIVE CARE MEDICINE 13:3 115 Ó 2012 Elsevier Ltd. All rights reserved.