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The specific objectives of this lecture are to: 1. which are used for transporting thermal energy from one location to other. for whate ver reason. Compare different refrigerants and sug gest replacements for CFCs and HCFCs 26. and serviceability e tc. secondary refrigerants are those liquids. depend very much on the type of refrigerant selected for a given application . Primary refrigerants are those fluids. the selection of sui table refrigerant has become one of the most important issues in recent times. for example in vapour compression and vapour absorption refrigeration systems. When used in compression or absorption systems. Discuss the importance of selection of suitable refrigerant in a refrigeratio n system (Section 26.4) 5. initial and operating costs. Of Version 1 ME. environmental and economic properties (Section 26. and discuss the important differences between primary and secondary refrigerants (S ection 26. 26. safety. Secondary refrigeran ts are also known under the name brines or antifreezes. Discuss refrigerant selection criteria based on thermodynamic. is an expensive proposition as it may call for several changes in th e design and manufacturing of refrigeration systems.2) 3. However. which are used dire ctly as working fluids. IIT Kha ragpur 2 . R eplacement of an existing refrigerant by a completely new refrigerant. List the criteria used in selecting refrigerants 4. these flu ids provide refrigeration by undergoing a phase change process in the evaporator . Describe the numbering system used for designating refrigerants (Section 26. List important thermodynamic and env ironmental properties influencing refrigerant selection 5. Differentiate between primary and secondary refrigerants 3. the student should be able to: 1.3) 4. Primary and secondary refrigerants: Fluids suitable for refrigeration purposes can be classified into primary and se condary refrigerants. As the name implies.1.2. Classify refrigerants into primary and secondary. However. Due to several environmental issues such as ozone layer depletion and global w arming and their relation to the various refrigerants used. important practical issues such as the system desi gn. t hermophysical. reliability. Introduction: The thermodynamic efficiency of a refrigeration system depends mainly on its ope rating temperatures. size. in this lecture the attention is mainly focused on those fluids that can be used as refrigerant s in vapour compression refrigeration systems only. Air used in an air cycle refrig eration system can also be considered as a refrigerant. In pr inciple. any fluid can be used as a refrigerant.1) 2. Present a comparison between different refrigerants (Section 26. Write the chemical fo rmula of a refrigerant from its number 6.5) At the end of the le cture. Hence it is very important to understand the issues related to the selection and use of refrigerants. Explain the importance of refrigerant s election 2.
condenser etc.1. for example in large air conditioning systems. as the operating pressures. Refrigerant selection criteria: Selection of refrigerant for a particular application is based on the following requirements: i. the discharge pressure should be as small as possible to allow light-wei ght construction of compressor. The concentration at which a lowest temperature can be reached without so lidification is called as eutectic point.3. iii.course. in an absorption refrigeration system. These solutions are known under the general name of brines. the secondary refrigerants do not undergo ph ase change as they transport energy from one location to other. Unlike primary refrigerants. The commonly used secondary refrigeran ts are the solutions of water and ethylene glycol. 26. if the operating temperatures are above 0oC. In this lec ture attention is focused on primary refrigerants used mainly in vapour compress ion refrigeration systems. the saturation pressure shou ld be above atmospheric for prevention of air or moisture ingress into the syste m and ease of leak detection. c) Pressure ratio: Should be as s mall as possible for high volumetric efficiency and low power consumption d) Lat ent heat of vaporization: Should be as large as possible so that the required ma ss flow rate per unit cooling capacity will be small The above requirements are somewhat contradictory. the freezing point of a brine will be lower than the freezing point of its constituents. then pure water can also be used as secondary refrigerant. A ntifreezes or brines are used when refrigeration is required at sub-zero tempera tures.3. Thermodynamic and thermo-physical properties: The requirements are: a) S uction pressure: At a given evaporator temperature. propylene glycol or calcium c hloride. a refrigerant and absorbent combination is used as the working fluid. The temperature at which freezing of a brine takes place its depends on its concentr ation. and Economics 26. IIT Kharagpur 3 . temperatures and latent heat of vaporization are related by ClausiusClapeyron Equation: ln (Psat ) = − h fg RT + s fg R (26. As discussed earlier. Higher suction pressure is better as it leads to s maller compressor displacement b) Discharge pressure: At a given condenser tempe rature. Generally.1) Version 1 ME. An important pro perty of a secondary refrigerant is its freezing point. Thermodynamic and thermo-physical properties Environme ntal and safety properties. ii.
from the above equation it can be shown that: ⎡ h fg Pc = exp ⎢ Pe ⎢R ⎣ ⎛1 1 ⎜ ⎜T − T c ⎝e ⎞⎤ ⎟⎥ ⎟ ⎠⎥ ⎦ (26.In the above equation. The normal boiling point indicates the useful temp erature levels as it is directly related to the operating pressures. Psat is the saturation pressure (in atm. Tc and Te are condenser and evaporator temperatures. hfg and sfg are enthalpy and entropy of vaporization and R is th e gas constant. On the other hand since the vapour pressure will be low whe n critical temperature is high. the volumetric capacity will be lower for refrig erants with high critical temperatures. Hence a trade-of f is required between the latent heat of vaporization and pressure ratio. From the above equation. The important properties such as l atent heat of vaporization and specific heat depend on the molecular weight and structure of the molecule.2) In the above equation.7. the pressure ratio also increases. Trouton’s rule shows that the latent heat of vaporizati on will be high for refrigerants having lower molecular weight. mo lecular weight and structure. Pc and Pe are the condenser and evaporator pressures. Thus the normal boiling point is a good indicator of the critical temperature of the refrigerant. IIT Kharagpur 4 . In add ition to the above properties. Since the change in entropy of vaporization is relatively small. the following properties are also important: e) I sentropic index of compression: Should be as small as possible so that the tempe rature rise during compression will be small f) Liquid specific heat: Should be small so that degree of subcooling will be large leading to smaller amount of fl ash gas at evaporator inlet g) Vapour specific heat: Should be large so that the degree of superheating will be small h) Thermal conductivity: Thermal conductiv ity in both liquid as well as vapour phase should be high for higher heat transf er coefficients i) Viscosity: Viscosity should be small in both liquid and vapou r phases for smaller frictional pressure drops The thermodynamic properties are interrelated and mainly depend on normal boiling point. it ca n be seen that for given condenser and evaporator temperatures as the latent hea t of vaporization increases. A high crit ical temperature yields higher COP due to smaller compressor superheat and small er flash gas losses.) at a temperatur e T(in Kelvin). critical temperature. This once again shows a need for trade-o ff between high COP and high volumetric capacity. It is observed that for most o f the refrigerants the ratio of normal boiling point to critical temperature is in the range of 0.6 to 0. The specific hea t of refrigerant is related to the structure of the molecule. If specific heat o f refrigerant vapour is low then the shape of the vapour dome will be such that the compression process starting with a saturated Version 1 ME.
The freezing point of the refrigerant should be lower than the lowest operating temperature o f the cycle to prevent blockage of refrigerant pipelines. However.. However. a small value of vapour specific heat indicates higher degree of super heat. e. the environmental and safety properties are very important. IIT Kharagpur 5 . the ODP of refrigerants should be zero. c) Total Equivalent Warming Index (TEWI): The factor TEWI considers both direct (due to release into atmosphere) and indirect (through ene rgy consumption) contributions of refrigerants to global warming.2. phosgene-COCl2). all fluids other than air can be called as toxic as the y will cause suffocation when their concentration is large enough. Some fluids are toxic even in small concentrations. R 11. which becomes meaningful only when the degree of concentrat ion and time of exposure required to produce harmful effects are specified. Some refrigerants such as CFCs and HCFCs are non-toxic when mixed with air in normal condition. Since vapour and liquid specific heats are also related. at present the environment friendliness of the refrigerant is a major factor in deciding the us efulness of a particular refrigerant.e. CFCs and HCFCs) or bromine cannot be used under the new regulations b) Global Warming Potential (GWP): Refrigerants should have as low a GWP value as possible to minimize the problem of global warming. Some fluids are mildly toxic. refri gerants having either chlorine (i. a large value of vapour specific heat results in a higher value of liquid specific heat.g. R134a) are likely to be regulated in future. they decompose forming highly toxic elemen ts (e. refrigerants used in a refrigeration system shou ld be nontoxic. Thus toxicity is a relative term. d) Toxicity: Ideally..e.. ref rigerants with as a low a value of TEWI are preferable from global warming point of view. R22).g. and Maintenance condition Version 1 ME. leading to higher flash gas losses. R 12) or will be phased-out in near-future(e. i. when they come in contact with an open fl ame or an electrical heating element. The important environmental and safety pro perties are: a) Ozone Depletion Potential (ODP): According to the Montreal proto col. Environmental and safety properties: Next to thermodynamic and thermophysical properties. Naturally. 26. they should be non-ozone depl eting substances. In fact. Refrigerants having non-zero ODP have either already been phas ed-out (e. they are dangerous only when the concentration is large and duration of expo sure is long.g. However. Refrigerants with zero ODP but a high value of GWP (e.e. Since O DP depends mainly on the presence of chlorine or bromine in the molecules.K. Studies show that in general the optimum value of mo lar vapour specific heat lies in the range of 40 to 100 kJ/kmol.point terminates in the superheated zone (i. compression process will be dry).g. In general the degree of hazard depends on: Amount of refrigerant used vs total space Type of occupancy Presence of open flames Odor o f refrigerant. i.3.
molecular weight etc. For flammable refrigerants special prec autions should be taken to avoid accidents. i) Fully saturated. the usefulness of a particular refrigerant dep ends on the specific application. Other important properties are: f) Chemical stability: The refrigerants shoul d be chemically stable as long as they are inside the refrigeration system. ASHRAE has divided refrigerants into six safety groups (A1 to A3 and B1 to B3). it should be easy to detect the leaks. R11. All the refrigerants are designated by R followed by a un ique number.g. From the number one can get some useful information about the type of refrigerant.g. R134a. ammonia). Designation of refrigerants: Figure 26. Based on the above criteria. These refr igerants are designated by R XYZ. R22. IIT Kharagpu r 6 .3.1 shows the classification of fluids used as refrigerants in vapour co mpression refrigeration systems. For these systems the refrigerants should have as high a dielectric strength as possible j) Ease of leak detection: In the event of leakage of refrigerant f rom the system.4. while refrigerants belonging to Group B3 (e.3. its chemical composition. Since a large number of refrigerants have been developed over the years for a wide variety of applications. where: X+1 indicates the number of Carbon (C) atoms Y-1 indicates number of Hydrogen (H) atoms. e) Flammability: The refrigerants should prefe rably be non-flammable and nonexplosive. and Version 1 ME. 26. Refrige rants belonging to Group A1 (e. a numbering system has been adopted to designate various refrigerants.g. Refrigerants that ar e completely miscible with oils are easier to handle (e. ethane (C2H6). Economic properti es: The refrigerant used should preferably be inexpensive and easily available. However. for re frigerants with limited solubility (e.g. R 22) special precautions should be tak en while designing the system to ensure oil return to the compressor i) Dilelect ric strength: This is an important property for systems using hermetic compresso rs. g) C ompatibility with common materials of construction (both metals and nonmetals) h ) Miscibility with lubricating oils: Oil separators have to be used if the refri gerant is not miscible with lubricating oil (e. 26. R12).Thus from toxicity point-of-view. R1140) are most hazardou s.g. halogenated compounds: These refrigerants are d erivatives of alkanes (CnH2n+2) such as methane (CH4). R744. R718) are least ha zardous. R12.
of Hydrogen atoms = 2-1 = 1 Z = 2 ⇉ No. ∴ the designation is R 717 Molecular weight is 44.g. molecules having same chemical composition but different atomic arrangement. of (H+F) atoms = 4-1-2 = 1 ⇉ No. e. Ex. of Fluorine at oms = 2 The balance = 4 – no. of Chlorine atoms = 1 ∴The chemical formula of R 22 = CHClF2 Similarly it can be shown that the chemica l formula of: R12 R134a = = CCl2F2 C2H2F4 (derivative of ethane) (letter a stands for isomer. Only 2 digits indicates that the value of X is zero. ∴ the designation is R 744 Molec ular weight is 18. ∴ the designation is R 718 Version 1 ME. IIT Kharagpur 7 . e.: Ammonia: Carbon dioxide: Water: Molecular weight is 17. R134 and R134a) ii) Inorganic refrigerants: These are designated by number 7 followed by the molecular weight of the refrige rant (rounded-off).g.Z indicates number of Fluorine (F) atoms The balance indicates the number of Chlorine atoms. of Carbon atoms = 0+1 = 1 ⇉ derivative of methane (CH4) Y = 2 ⇉ No. Ex: R 22 X = 0 ⇉ No.
Az eotropic mixtures: R 500: Mixture of R 12 (73.Zeotropic Synthetic Natural . R 125 (40%) and R 134a (40%) R407B : Mixture of R 32 (10%).HFCs .2%) R 502: Mix ture of R 22 (48.Azeotropic . R 143a (52%) and R 134a (4%) R407A : Mixture of R 32 (20%).8 %) and R 115 (51.Inorganic o NH3 o CO2 o H2O Fig.HCFCs .g.CFCs .Organic (HCs) . where as zeotro pic refrigerants (e. IIT Kharagpur 8 .Refrigerants Pure fluids Mixtures .26.8 %) and R 152a (26. R 125 (70%) and R 134a (20%) R410A : Mixture of R 32 (50%) and R 125 (50%) Version 1 ME.2%) R503: Mixture of R 23 (40.9%) R507A: Mixture of R 125 (50%) and R 143a (50%) Zeotropic mixtures: R404A : Mixture of R 125 (44%).1 %) and R 13 (59. non-azeotropic mixtures) are designated by 400 series.1: Classification of fluids used as refrigerants iii) Mixtures: Azeotropic mixtures are designated by 500 series.
most of the conventional sy nthetic refrigerants also cause significant global warming.iv) Hydrocarbons: Propane (C3H8) n-butane (C4H10) : : R 290 R 600 R 600a R1150 ( C2H4) R1270 (C3H6) iso-butane (C4H10) : Unsaturated Hydrocarbons: 26. R 12 (CFC 12). the synthetic refrig erants face an uncertain future. Of th ese.5. The scenario changed completely after the discovery of ozone layer depletion in 1974. R 22 (HCFC 2 2). However. Since ozone layer depletion cou ld lead to catastrophe on a global level. opinions differed on rep lacements for conventional refrigerants. The synthetic replacements for t he older refrigerants are: R-134a (HFC-134a) and blends of HFCs. R 12 was used primarily in small capacity refrigeration and cold sto rage applications. which somewhat restricts its application. except ammonia. HCFCs etc. However. This is also one of the oldest known refrigerants. Ammonia has good ther modynamic. The dep letion of stratospheric ozone layer was attributed to chlorine and bromine conta ining chemicals such as Halons. all the other refrigerants used in cold storages had to be phased-out and a search for suitable replacements began in earnest. Among the refrigerants used. In view of the envir onmental problems caused by the synthetic refrigerants. while the other refrigerants were used in large systems such as large air conditioning plants or cold storages. it has been very widely used due to its excellent thermodynamic and thermophysical properties. Generally. th ey are being studied widely and are likely to play a prominent role in future. Though th ese refrigerants have some specific problems owing to their eco-friendliness. R 22. it is toxic and is not compatible with some of the common materials of construction such as cop per. The most commonly used natural refrigerant is a mmonia. The alternate refrigerants can be class ified into two broad groups: Version 1 ME. IIT Kharagpur 9 . thermophysical and environmental properties. these refrigerants have to be phased ou t due to their Ozone Depletion Potential (ODP). P rior to the environmental issues of ozone layer depletion and global warming. R 502 and ammonia. Other natural refrigerants that a re being suggested are hydrocarbons (HCs) and carbon di-oxide (R-744). As a result except ammon ia. synt hetic refrigerants are non-toxic and non-flammable. cold storage a nd air conditioning applications are: R 11 (CFC 11). it has been agreed by the global commu nity to phase out the ozone depleting substances (ODS). compared to the nat ural refrigerants the synthetic refrigerants offer lower performance and they al so have higher Global Warming Potential (GWP). th e most widely used refrigerants were: R 11. Comparison between different refrigerants: Synthetic refrigerants that were commonly used for refrigeration. all the other refrigerants are synthetic refrigerants and are no n-toxic and non-flammable. As a result. Though ammonia is toxic. R 502 (CFC 12+HCFC 22) etc. CFCs. At the same time. R 11 was primarily used with centrifugal compressors in air conditioning ap plications. However. R 12. it was also observed that in addition to ozone layer depletion.
carbon dioxide. hydrocarbons and t heir blends It should be noted that the use of natural refrigerants such as carbon dioxide. and it is also important take precautions to prevent le akage. most of these blends are non-azeotropic i n nature. unlike the HFC based refrigerants. Another important advantage is that they are completely environment friendly. but is a revival of the once-used-anddiscar ded technologies in a much better form. However. hydrocarbons is not a new phenomena.i) ii) Non-ODS. Table 26. IIT Kharagpur 10 . The alternate synthetic refrig erants are normally non-toxic and non-flammable. one advantage of using them is that they are familiar in terms of their strengths and weaknesses.1 shows a li st of refrigerants being replaced and their replacements. Version 1 ME. as this will change the composition of the mixture. Since the natural refrigerants are essen tially making a comeback. It is also possible to use blen ds of various HFCs to obtain new refrigerant mixtures with required properties t o suit specific applications. whi ch do have considerable global warming potential. as a result there could be significant temperature glides during evapo ration and condensation. synthetic refrigerants based on Hydro-Fluoro-Carbons (HFCs) and their b lends Natural refrigerants including ammonia.
0 R 744 (CO2) NBP = -78.06oC Cp/Cv = 1.05 o Air conditioning systems Cold storages GWP = 1500 R 134a (HFC) NBP = -26.N) R 227ea (N) R 401A.0 o Cold storages Ice plants Food processing Frozen food cabinets No replacement required * Toxic and flammable * Incompatible with copper * Highl y efficient * Inexpensive and available GWP = 0.4 C hfg at 40oC=321.N) R 411A.02oC Cp/Cv = 1. water coolers. IIT Kharagpur 11 .R 507A (R.98oC Cp/Cv = 1.3 kJ/kg Tcr =31.N) R 404A (R.1oC Cp/Cv = 1.8 kJ/kg Tcr =112.N) R 407C (R.0 o Cold storages No replacement required Air conditioning systems * Very low critic al temperature Simultaneous cooling and * Eco-friendly heating (Transcritical cy cle) * Inexpensive and available GWP = 1.N) R 134a (R.0oC Cp/Cv = 1.8 C hfg at NBP=165.9 kJ/kg Tcr =133. their applications and substitutes Version 1 ME.N) R 141b (N) R 245fa (N) n-pe ntane (R.R 401B (R.31 ODP = 0.15 C hfg at NBP=222. automobile A/Cs etc * Immiscible in mineral oils * Highly hygrosc opic GWP = 1200 R 717 (NH3) NBP = -33.2 kJ/kg Tcr =96.5 kJ/kg Tcr =197.R 411B (R.0 Table 26.5 kJ/kg Tcr =101.35 C hfg at NBP=1368.0 o Domestic refrigerators Small air conditioners Water coolers Small cold storages R 22 (R.1: Refrigerants.0 o Application Large air conditioning systems Industrial heat pumps As foam blowing agent Substitute suggested Retrofit(R)/New (N) R 123 (R. N) R 717 (N) GWP = 7300 R 22 (HCFC) NBP = -40.102 ODP = 0.Refrigerant R 11(CFC) NBP = 23.3 ODP = 0.N) R 71 7 (N) R 410A. R 410B (N) R 417A (R.04oC Cp/Cv = 1.13 ODP = 1.N) GWP = 3500 R 12 (CFC) NBP = -29.8 C hfg at NBP=233.7 C hfg at NBP=182.126 ODP = 1.166 ODP = 0.N) R 507.0 o Used as replacement for R 12 No replacement required in domestic refrigerators.
0 o Application Absorption systems Steam jet systems Substitute suggested Retrofit(R)/New (N) No replacement required * High NBP * Hi gh freezing point * Large specific volume * Eco-friendly * Inexpensive and avail able No replacement required * Flammable * Eco-friendly GWP = 1.: a) and d) Version 1 ME.0 o Replacement for R 12 Domestic refrigerators Water coolers GWP = 3.086 ODP = 0.0oC Cp/Cv = 1. Which of the following statements are TRUE? a) A primary refrigerant does not undergo phase change in a refrigeration cycle b) A secondary refrigerant does n ot undergo phase change in a refrigeration cycle c) The freezing point of a brin e is generally lower than the freezing point of its constituents d) The freezing point of a brine is generally higher than the freezing point of its constituent s Ans.9 kJ/kg Tcr =374.1: Refrigerants.15oC Cp/Cv = 1.0 Table 26. C hfg at NBP=2257.) Questions and answers: 1.0 R600a (iso-butane) NBP = -11. IIT Kharagpur 12 .Refrigerant R718 (H2O) NBP = 100. their applications and substitutes (contd.: b) and c) 2.73 C hfg at NBP=367.33 ODP = 0.7 kJ/kg Tcr =135. Which of the following statements are TRUE? a) The suction pressure of a refrigerant should be as high as possible b) The suction pressure of a refrigerant should be as low as possible c) The discharge pressure of a ref rigerant should be as high as possible d) The discharge pressure of a refrigeran t should be as low as possible Ans.
Which of the following statements are TRUE? a) A refrigerant having volumetric capacity b) A refrigerant having volumetric capacity c) A refrigerant having vo lumetric capacity d) A refrigerant having volumetric capacity Ans. The c hemical formula of refrigerant R11 is: a) CCl3F b) CClF3 c) CClHF d)CHF Ans. the compressor discharge temperature increases Ans.: a). the saturation pressure decreases b) For given evaporator and condenser temperatures. IIT Kharagpur 13 . Which of the following statements are TRUE? a) At a given temperature. a refrigerant having high vapour specific heat may give rise to wet compressio n d) For saturated state at the inlet to the compressor. c) and d) 4 .: a) high critical temperature yields high COP and high high critical temperature yi elds low COP and high high critical temperature yields low COP and low high crit ical temperature yields high COP and low Version 1 ME. as the isentropic index of compression increases. the pressure ratio decreases c) As the latent heat of vaporization i ncreases. Which of the following statements are TRUE? a) Low molecular weight refrigerants have high latent heat of vaporization b) Low molecular weight refrigerants have low l atent heat of vaporization c) For saturated state at the inlet to the compressor .: d) 5. as the latent heat of vaporization increases. becomes smaller for a give n capacity d) For a given pressure ratio. the required mass flow rate of refrigerant. as the latent heat of vaporization increases. a refrigerant having lo w vapour specific heat may give rise to wet compression Ans.3.: a) and c) 6.
The chemical formula of R141 is: a) C2H3ClF3 b) C2H2Cl3F c) C2H3Cl2F d) C2H2C lF3 Ans. Which of the following refrigerants replace R12 in domestic refri gerators? a) R22 b) R11 c) R134a d) R141b Ans. Which of the following re frigerants are suggested as replacements for R22 in large air conditioning and c old storage systems? a) R134a b) R21 c) R410A d) R407C Ans.: a) and d) 9. b) and c) 10.: c) 11. Which of the following refrigerants are phased-out due to Montreal protocol on ozone layer depletion a) R11 b) R21 c) R12 d) R32 Ans. IIT Kharagpur 14 .: a). Which of the following statements is TRUE? a) Evaporation proces s is non-isothermal for zeotropic mixtures b) Evaporation process is non-isother mal for azeotropic mixtures c) Composition of azeotropic mixture changes in the event of a leak d) Composition of zeotropic mixture changes in the event of a le ak Ans.7.: c) 8.: c) and d) Version 1 ME.
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