SAE TECHNICAL PAPER SERIES

2001-01-0154

Thermochemical Characteristics of Dimethyl Ether An Alternative Fuel for Compression-Ignition Engines

Ho Teng, James C. McCandless and Jeffrey B. Schneyer
AVL Powertrain Technologies, Inc.

Reprinted From: New Developments in Alternative Fuels for CI Engines (SP1608)

SAE 2001 World Congress Detroit, Michigan March 5-8, 2001

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2001-01-0154

Thermochemical Characteristics of Dimethyl Ether An Alternative Fuel for Compression-Ignition Engines

Ho Teng, James C. McCandless and Jeffrey B. Schneyer
AVL Powertrain Technologies, Inc.

Copyright 2001 Society of Automotive Engineers, Inc.

ABSTRACT This paper analyzed chemical and thermophysical properties of dimethyl ether (DME) as an alternative fuel for compression-ignition engines. On the basis of the chemical structure of DME and the molecular thermodynamics of fluids, equations have been developed for most of the DME thermophysical properties that would influence the fuel-system performance. These equations are easy to use and accurate in the pressure and temperature ranges for CI engine applications. The paper also pointed out that the DME spray in the engine cylinder would differ significantly from that of diesel fuel due to the thermodynamic characteristics of DME. The DME spray pattern will affect the mixing and combustion processes in the engine cylinder, which, in turn, will influence emissions from combustion.

properties of DME, especially in the subcooled-liquid region. Although accurate thermophysical properties may be obtained only experimentally, because DME is a simple pure substance from the thermodynamic viewpoint, the existing molecular thermodynamic theory [8,9] can predict most of its properties with accuracy for the industrial standard (errors 5%). This paper presents a molecular-thermodynamic study on those of DME properties related to the fuel-system design and modeling.

CHEMICAL CHARACTERISTICS OF DME CHEMICAL STRUCTURE OF DME Most of the thermochemical properties of a pure fluid are closely related to its chemical structure. Therefore, it may be helpful to review the chemical structure of DME before the study of the structure-related properties. The chemical formula of DME is CH3-O-CH3 and its chemical structure is shown in Fig.1. Although the oxygen atom in DME has only two C-O bonds, being a member of the VIfamily elements, the oxygen atom has six outermostlayer electrons; and, plus the two shared electrons with the carbon atoms, the outermost layer of the oxygen atom has a total of eight electrons. According to the octet

INTRODUCTION Many investigators have demonstrated that dimethyl ether (DME) has a high cetane number and low emissions from combustion [1-5]. These good thermochemical characteristics make DME a promising alternative fuel for compression-ignition engines. However, because the largest use of DME is as a propellant in aerosol engineering to date, the thermophysical properties of DME are still not fully understood. The properties reported in the literature were vapor pressures and few properties at low pressures and room temperatures [6,7]. As a fuel for CI engines, the subcooled-liquid properties, such as density, viscosity, compressibility/bulk-modulus, etc., are of great importance in design and modeling of the DME fuel system. Because DME has a poor lubricity and a high compressibility in comparison to diesel fuel, none of the existing fuel systems can be applied directly to the DME application. The fuel system for DME must be specially designed according to its characteristics. Therefore, a good understanding is necessary of the thermophysical

H H C H O H C

Orbitals of lone- electron pairs

Fig.1 Chemical structure of dimethyl ether.

rule (the Lewis structure), these eight electrons form four orbitals: two orbitals for the two pairs of shared electrons forming the C-O bonds and two orbitals for the two pairs of lone electrons. The electrostatic repulsion between any two pairs of electrons tends to make them as far apart as possible; and, as a net effect, all of the orbital angles become the same. If each pair of the lone electrons is imagined to be associated with a pseudo atom, then the four (two real plus two pseudo) atoms associated with the oxygen atom through the orbitals form a symmetrical shape of a regular tetrahedron a 3-D figure with four equilateral-triangle faces: with the oxygen atom at the center and the other four at the four corners, and all the orbitals at 109.5 angles to each other. In reality, the orbital angles cannot be exactly 109.5 due to intra-molecular forces and they may depart from the perfect tetrahedral angle a few degrees. For example, the angle between the two C-O bonds is actually 112 [10]. Carbon belongs to the IV family and it has four electrons in its outermost layer. In alkanes and radicals of alkanes, the carbon atom forms four bonds through association with four other atoms; thus, it also has eight electrons in its outermost layer. Each of the carbon atoms in alkanes and radicals of alkanes is associated with a tetrahedron with the carbon atom at the center and the four associated atoms at the four corners. This leads to a reasonable prediction that angles between C-H bonds in the methyl radicals in DME are 109.5 this prediction is accurate enough: the actual angles are 108 [10]. The similar features of the oxygen and carbon atoms suggest that the chemical structure of propane (its chemical formula is CH3-CH2-CH3) should be very similar to that of DME. The chemical structure of propane is shown in Fig.2. Indeed, if the oxygen atom is replaced with a carbon atom and the two pseudo atoms associated with the oxygen atom are replaced with two hydrogen atoms, then the chemical structure of DME turns into that of propane. In propane, the angle between the two C-C bonds remains 112 [10]. However, because of changes in intra-molecular forces, angles between C-H bonds become 107 [10]. It is seen in Figs. 1 and 2 that, although both propane and DME are often mentioned as straight-chain molecules in the literature, actually, their chains are zigzag due to the tetrahedral bonding nature of the carbon and oxygen

atoms in them. The C-O bond length in DME (1.42 ) is shorter than the C-C bond length in propane (1.53 ) [10] and the C-O bond energy (351 kJ/mol) is larger than that of the C-C bond (341 kJ/mol) [11]; thus, intra-molecular forces in a DME molecule may be larger than those in a propane molecule. However, because two of the four corners of the oxygen-atom-centered tetrahedron are not actually associated with atoms, the angle between the two C-O bonds is flexible; and, the two C-O bonds are often under the distortion from the two methyl radicals, which significantly weakens the stability of the chemical structure of DME. Because the function group that characterizes DME (Fig.3) is not chemically active, DME is often considered to be inert chemically.

C O

Fig.3 The function group of DME.

Due to the polarity induced by the two pairs of lone electrons of the oxygen atom in the DME molecule, the inter-molecular forces in DME are greater than in propane (noting that propane is a non-polar fluid). The intra-molecular forces influence the chemical characteristics while the inter-molecular forces affect thermodynamic properties. It is difficult to predict the combustion characteristics solely on the basis of the chemical structure and intra-molecular forces because combustion of an organic fuel undergoes a complicated chain reaction. However, it is possible to predict some of thermophysical properties on the ground of the molecular structure and inter-molecular forces. Large intermolecular forces lead to strong attractions among interacting molecules in a liquid fluid. Thus, it takes more energy for a DME molecule than a propane molecule to overcome attractive forces from neighboring molecules to travel from the liquid phase to the vapor phase. As a result of the stronger molecular attraction, DME has a higher critical temperature, a higher normal boiling point, and larger latent heat and saturated-liquid density at a normal temperature (e.g., at 20 C) than propane does. And, due to the same reason, propane has a higher vapor pressure than DME does at the same temperature [4]. HEAT OF COMBUSTION OF DME

H H C H H C H H C

Because DME is a pure substance, the heat of combustion of DME can be calculated accurately on the basis of the following chemical reaction: C2H6O (l,g) + 3O2 (g) 2CO2 (g) + 3H2O (g), (1)

Fig.2 Chemical structure of propane.

where l = liquid and g = gas, indicating the states of reactants and products. The heat release from DME combustion described by Eq.(1) is
Tem perature ( C)

1000

900

QC = R n i H i P n i H i ,

(2)

800

Total ignition delay

700

where R and P indicate reactants and products, and ni and Hi are, respectively, the mole number and formation enthalpy of the ith substance. Following the tradition, the heat of DME combustion is considered at the standard state (1 atm and 25 C). At this state, formation enthalpies of CO2 (g), H2O (g), DME (g) (DME is a gas at the standard state), and O2 (g) are, respectively, HCO2 = 393.51 kJ/mol, HH2O = 241.87 kJ/mol, HDME = 184.10 kJ/mol, and HO2 = 0 kJ/mol (by convention, formation enthalpy of a stable element is zero) [10]. Substituting these values into Eq.(2) the heat of combustion of DME is obtained as
QC = HDME + 3HO2 2HCO2 3HH2O

600

500

Chemical Physical delay delay

400

300 0 1 2 3 4 5 6 7 8 9 10

Tim e (m s)

Fig.4 A typical cylinder-temperature history showing the compression-ignition delay [12].

= 1328.53 kJ/mol = 28.88 MJ/kg

(3)

Considering that, in reality, oxygen is from air and that every 4.76 moles of air contains 1 mole oxygen, Eq.(1) may be rewritten as C2H6O (l,g) + 3 [O2 (g) + 3.76 N2 (g)]
2CO2 (g) + 3H2O (g) + 3 3.76 N2 (g). (4)

ignite the air-fuel mixture. The ignition delay, as shown in Fig.4 for a case reported in the literature [12], has two stages. The first stage is the physical delay, which is due to the fuel evaporation, mixing, and establishment of the critical concentration of radicals for initiation of the chain reaction; because the heat release of the earlystage, unsteady reactions are just enough to balance the heat dissipation, physical processes are predominant and there is no apparent temperature rise. The second stage is the chemical delay, which is associated with the subsequent steady chain reaction and is the time for the air-fuel mixture to reach the chain explosive condition. Because the critical temperature of DME is only 127 C, which is lower than the compressed-air temperature at the later stage of the compression stroke, the DME injected into the cylinder may vaporize immediately due to the fact that a liquid phase is thermodynamically unstable above the critical temperature. When the temperature of DME is greater than 127 C, DME becomes a superheated gas and, therefore, no evaporation is associated during mixing. The chain reaction of the DME combustion may be initiated by either (or both) of the two competing pathways [12,13]: C-O bond fission (pyrolysis mechanism): CH3OCH3 CH3O + CH3; Hydrogen abstraction (oxidation mechanism): CH3OCH3 + O2 CH3OCH2 + HO2, CH3OCH2 CH2O + CH3. (8) (9) (7)

Although Eq.(4) is equivalent to Eq.(1) in the sense of chemical reaction, it offers information on the air/fuel ratio. It is seen from Eq.(4) that complete combustion of 1-mol DME requires 3 (1 + 3.76) = 14.28-mol air. Thus, the air/fuel ratio at the stoichiometric condition is (A/F)ST = 14.28 mol-air/mol-DME. (5)

Noting that the molar mass of air = 28.97 g/mol = 28.97 kg/kmol and the molar mass of DME = 46 g/mol = 46 kg/kmol, (A/F)ST can be given alternatively as (A/F)ST = 8.99 kg-air/kg-DME. (6)

Equation (6) indicates that complete combustion of 1-kg DME requires much less air than that of 1-kg gasoline or diesel fuel at the stoichiometric condition. CETANE NUMBER OF DME The cetane number of a fuel measures its compression-ignition quality. For a given fuel, the higher its cetane number, the better its compression-ignition quality. The compression-ignition quality of a fuel may be characterized by the time lag between the start of fuel injection and the commence of ignition. This ignition delay is due to that it takes a certain period of time for the fuel injected into the compressed air in the engine cylinder to reach a temperature that is high enough to

The C-O bond energy is smaller than that of the C-H bond (414 kJ/mol [11]) and the distortion of the C-O bonds in the DME molecule weakens the bonding strength; thus, the C-O bond breaks easier than the C-H bond. Therefore, the pyrolysis mechanism may be more

possible to start the chain reaction of the DME combustion at relatively low temperatures. Because DME has a low critical temperature and the C-O bond in DME breaks easily, the physical delay of DME is much shorter than many conventional fuels, resulting in a short total ignition delay. The short ignition delay of DME leads to a high cetane number: the cetane number of DME is greater than 55 [3,14]. In comparison, the cetane number of diesel fuel falls in a range between 40 and 54 [15]. EMISSIONS FROM DME COMBUSTION Carbon monoxide (CO), unburned hydrocarbons (HC), oxides of nitrogen (NOx, comprised of NO and NO2) and particulate matter (PM) are emissions that are regulated for compression-ignition engines. Many investigators have demonstrated that emissions of these pollutants from DME combustion are significantly lower than those from diesel combustion [1-3,5,14]. Emissions from DME combustion are analyzed in the following. CO is an intermediate product from incomplete combustion and HC emissions consist of partially or completely unburned fuel. Therefore, both CO and HC are resulted from fuel-rich combustion and they can be reduced significantly under stoichiometric or lean-fuel combustion. Although a CI engine operates with an overall lean mixture, its combustion is non-homogeneous and, thus, both CO and HC are produced in locations where the combustion takes place under a fuel-rich condition due to incomplete air-fuel mixing. Because only mixtures within combustible limits (for DME, lean limit = 3.4 vol% and rich limit = 27 vol% [16]) will burn, the over-rich and over-lean mixture formed during the fuel injection (ignition delay period) may escape the main combustion [15], resulting in the unburned fuel. DME has a short ignition-delay period; thus, it significantly reduces the HC emissions from the above mechanism. DME is an oxygenated fuel containing 35-wt% oxygen and has a good mixing characteristic due to that it basically is a superheated gas after entering the engine cylinder. Thus, the levels of the CO and HC emissions from DME combustion should be much lower than that from combustion of diesel fuel. The similarity in chemical structures of DME and propane suggests that the CO and HC emissions from DME combustion may be close to those from propane combustion [17]. NOx is not a direct fuel-combustion product but a side effect of combustion. Because nitrogen is basically chemically inert at temperatures lower than 1370 C [18], NOx formation requires a high temperature (T > 1370 C) and plentiful oxygen. Thus, the most favorable condition for NOx formation should be in the combustion stage from the start of combustion to the time when the peak temperature is reached. Any factors that influence the early-stage heat release will affect the NOx formation.

Shortening the ignition delay is one of such factors because it can reduce the amount of fuel burned in the pre-mixed burning stage and, therefore, it can reduce the peak temperature [15,18]. Because DME has a short ignition-delay period, this feature of DME tends to reduce the NOx formation. Note that although DME is an oxygenated fuel, the chance to release free oxygen is very limited as revealed by the DME chemical kinetics [12]; thus, the effect of the oxygen content in DME on NOx formation is negligibly small. PM consists of carbon particles, commonly known as soot, coated with absorbed and condensed organic compounds such as unburned hydrocarbon and oxygenated hydrocarbon. Soot forms by thermal pyrolysis during combustion and formation of soot requires a fuel-rich condition and a high temperature. A fast mixing before reaching the pyrolysis temperature will reduce the soot formation. The precursors of soot are the unsaturated carbons [16,19]. Acetylene (C2H2), ethylene (C2H4), and proparagyl (C3H3) are common unsaturated carbons in diesel-fuel combustion [19]. The percentage of fuel carbons that form soot precursors decreases with increase in the oxygen content in the fuel [19] and with decrease in the number of C-C bonds (the source of the unsaturated carbons) in the fuel [16]. The experimental evidence has shown that as the oxygen content in the fuel reaches approximately 25 30 wt%, virtually no soot is produced from the fuel combustion [19]. Because the oxygen content of DME is 35 wt% and there is no C-C bond in DME, the percentage of fuel carbons that form soot precursors in DME combustion is almost zero [19]. Overall, due to its thermochemical characteristics, DME is a clean alternative fuel for CI engines. With employing conventional emission-control techniques (e.g., injection rate shaping, EGR, etc.), DME can achieve ultra-low emissions [14].

THERMOPHYSICAL PROPERTIES OF LIQUID DME

Since only liquid properties of DME are involved in the fuel system design and modeling, the present study focuses on the liquid properties of DME. However, because DME is a low-boiling-point fluid, its vapor properties can be easily predicted using a generalpurpose equation of state (e.g., Peng-Robinson equation or Benedict-Webb-Rubin equation). A liquid fluid has a local structure although it is highly disordered globally. This local structure makes the thermophysical properties of a liquid fluid be dependent on the weight, shape, size, and polarity of the molecule of the fluid and on the inter-molecular forces in the fluid. The thermodynamic behavior of a liquid fluid is closely related to its properties at the critical point. On the basis of the critical properties and the molecular structure of the fluid, many of the liquid properties can be predicted.

The critical properties of DME and some parameters that help to characterize the behavior of DME are given in the following:
Vapor pressure (bar)

60

50

Critical temperature Tc : Critical pressure pc : Critical density c : Boiling point at 1 atm Tb : Acentric factor : Dipole moment D :

127 C 53.7 bar 3 259 kg/m - 24.9 C 0.192 1.3 debyes

40

30

20

10

On the basis of the above properties and the molecular thermodynamic theory, equations for basic properties of liquid DME were developed. These equations are given in the following. SATURATED LIQUID
Saturated liquid density (kg/m )

-40

-20

20

40
o

60

80

100

120

Temperature ( C)

Fig.5 Vapor pressures of DME at T = 40 120 C.

800 750
3

Vapor pressure An Antoine-type developed for DME: vapor-pressure equation was

700 650 600 550 500 450 400 -40

Log p = 1.73 + 2.49

T 127 , T + 244

(10)

Latent heat (kJ/kg)

where Log is the common logarithm function, p is the vapor pressure in bar and T is the temperature in C. Equation (10) gives a very good prediction of the DME vapor pressure in the temperature range T = 40 127 C in comparison with the data reported in the literature [6]. For example, the boiling point at 1 atm (= 1.013 bar) reported in the literature is 24.9 C [6,8,10] and the prediction by Eq.(10) is 24.8 C; at 127 C, Eq.(10) gives p = 53.7 bar, which is precisely the critical pressure of DME. Figure 5 shows the predicted DME vapor pressures. Density: saturated liquid Following a technique developed by Rackett [8], an equation was developed, for prediction of the saturatedliquid density of DME, as follows:
s = ref Z C

-20

20

40
o

60

80

100

Temperature ( C)

Fig.6 Saturated liquid density of DME.

550

500

450

400

350

300

250

(11)
3

200 -40

-20

20

40
o

60

80

100

Temperature ( C)

where s is the saturated-liquid density in kg/m , ref = 3 280.68 kg/m is a reference density for DME; Z c = 0.287 is the critical compressibility factor of DME; and = [(127 T) / 400] 2 / 7 is a temperature-dependent parameter, and T is the temperature in C. Equation (11) should be used in the temperature range between 40 and 100 C. It is well known that the saturated-liquid 3 density of DME at 20 C is about 660 kg/m (= 0.66 3 g/cc). The prediction given by Eq.(11) is s = 661 kg/m (= 0.661 g/cc) at 20 C. Dependence of the DME

Fig.7 Latent heat of DME.

density on temperature predicted by Eq.(11) is shown in Fig.6. Latent heat The latent heat of DME can be predicted using the Pitzer-acentric-factor correlation [8]. When applied to DME, this correlation can be written as

 HV = 511.18 (1 T r ) 0.354 + 151.79 (1 T r ) 0.456 , (12)

where HV is the latent heat in kJ/kg, Tr = (T + 273)/400 is the corresponding temperature, and T is in C. The suggested temperature range for application of Eq.(12) is T = 40 100 C. Values of the latent heat of DME at two temperatures reported in the literature are 468 kJ/kg at 24.9 C and 402 kJ/kg at 25 C [10]. At these temperatures Eq.(12) predicts HV = 460 kJ/kg (at 24.9 C) and HV = 397 kJ/kg (at 25 C). They are close enough for an industrial standard. The predicted HV = HV(T) relationship is given in Fig.7. Ethanol is isomeric with DME and both ethanol and DME can be expressed by the chemical formula C2H6O. The chemical structure of ethanol is shown in Fig.8. The

The surface tension of DME may be predicted using the Macleod-Sugden equation [8]:

= [P ( L V )/M]4,
-3

(13)

where is the surface tension in dyn/cm (= 10 N/m), P is the parachor of DME, M is the molar mass of DME in g/mol, and L and V are, respectively, the densities of saturated liquid and vapor of DME in g/cc. On the basis of the chemical structure of DME, (CH3)2O, the parachor of DME is obtained as P = [CH3-] + [-O-] + [-CH3] = 131.0, where [CH3-], [-O-], and [-CH3] represent contributions of the chemical groups forming DME. L can be given by Eq.(11). V may be calculated using the nd following 2 -order virial equation of state: = p /(ZRT ),
Z = 1 + Bp /(RT ),

(14) (15) (16)

(17)
8

H C H

H O C H H

B=

RTc 0 (f + f 1 ), pc

f 0 = 0.1445 0.330 / T r 0.1385 / T r 2

0.0121 / T r 0.000607 / T r ,
3

Fig.8 Chemical structure of ethanol.

f 1 = 0.0637 + 0.331/ Tr 2 0.423 / Tr3 0.008 / Tr8 , (18)

where R is the gas constant, Z is the compressibility factor, B is the second virial coefficient, and Tr = T / Tc is the corresponding temperature. Note that in using an equation of state and calculating corresponding temperatures, the temperature must be in the absolute scale; thus, in Eqs. (14)-(18), T and Tc are in K. The recommended temperature range for application of Eqs. (14)-(18) is T < 373 K (= 100 C). Since the measured surface tension of DME is not currently available, verification of Eq.(13) is conducted using diethyl ether (DEE) whose chemical formula is

oxygen atom in ethanol can possibly induce three hydrogen bonds (two lone-electron pairs as receivers and the proton of the hydrogen atom associated with it as a donor) [20]. Because the molecules in liquid ethanol are strongly associated with each other via hydrogen bonding, which is much stronger than the molecular interaction in DME, the thermodynamic behavior of ethanol differs significantly from that of DME. Due to the very strong inter-molecular forces in ethanol, the normal boiling point of ethanol is 78 C (103 C higher than that of DME!); thus, at the atmospheric pressure and normal temperatures, ethanol is a liquid while DME is a gas. Due also to the hydrogen bonding, the latent heat of ethanol is 942 kJ/kg at 25 C, which is 2.34 times of the latent heat of DME at the same temperature. This explains why ethanol has a cold-start problem when used as a fuel for IC engines. In comparison, the latent heat of DME at 25 C is close to that of gasoline [21]. And, because the C-C bond is weaker than the C-OH bond in ethanol, ethanol does not lose its OH group at the initial step of the chain reaction; thus, chemical characteristics of ethanol also differ significantly from those of DME. As an overall effect, the autoignition temperature of ethanol is much higher than that of DME [16]. Surface tension

0.025

0.020

Surface tension (N/m)

0.015

0.010

0.005

0.000 -40

-20

20

40
o

60

80

100

Temperature ( C)

Fig.9 Surface tension of DME.

Subcooled liquid density (kg/m )

(C2H5)2O. DME and DEE are the most similar ethers in the ether family except for that both the parachor and liquid density of DEE are larger than those of DME, which results in a larger surface tension for DEE at the same temperature. At 25 C, Eq.(13) predicts = 16.40 dyn/cm for DEE, which is basically the same as the surface tension for DEE given in the literature: = 16.47 dyn/cm [10]. Because DME and DEE have very similar chemical and thermodynamic behavior, Eq.(13) should predict reasonably accurate values for the surface tension of DME. Figure 9 shows the variation of the surface tension of DME with temperature.

850
3

800 750 700 650 600 550 500 50

100

150

200

250

300

350

400

450

500

550

Pressure (bar)

SUBCOOLED LIQUID Density: subcooled liquid Equation (14) also applies to subcooled liquid. In this study, the Lee-Kesler equation [8], which may be expressed in a generalized form as Z = Z(T, p, Tc, pc, , Zc), was used to calculate the compressibility factor Z for subcooled-liquid DME. The results can be represented by the following correlation: = T (T ) + 0.146p 7.37 10 5 p 2 , T (T ) = 690 1.72T , (19) (20)

Fig.10 Subcooled liquid density of DME: I, -20 C; G, 0 C;

L, 20 C; M, 40 C; N, 60 C; + , 80 C.

12000

Bulk m odulus of DM E (bar)

10000

8000

6000 4000

2000

where is the subcooled-liquid density in kg / m 3 , T is in

C, and p is in bar. For T 100 C, the above equation gives reasonably good predictions for pressures up to 550 bar. Selected values of predictions are presented in Fig.10.

0 50

100

150

200

250

300

350

400

450

500

550

Pressure (bar)

Fig.11 Bulk modulus of liquid DME: I, -20 C; G, 0 C;

L, 20 C; M, 40 C; N, 60 C; + , 80 C.

Bulk modulus The compressibility of a liquid, , is defined as

Speed of sound in liquid DM E (m /s)

1400

1200

1 1 ( )T = , p E

(21) Applying

1000

where E is the bulk modulus of the liquid. Eq.(14) into Eq.(21) yields Z p(Z/p )T , = Zp or E= Zp . Z p(Z /p )T

800

600

(22)

400 50

100

150

200

250

300

350

400

450

500

550

Pressure (bar)

(23)

Fig.12 Speed of sound in liquid DME: I, -20 C; G, 0 C;

L, 20 C; M, 40 C; N, 60 C; + , 80 C.

For any given temperature, the compressibility or bulk modulus of liquid DME can be solved by applying the Lee-Kesler equation into Eq.(22) or (23). The bulkmodulus calculations are represented by the following correlation:
E = E 0 + E 1 p,

E 0 = 4984 72.23T + 0.253T 2 , E 1 = 9.65,

(25) (26)

(24)

where E and p are in bar, and T is in C. Equations (24)(26) can give reasonably good predictions for

Speed of sound in liquid DM E (m /s)

temperatures between 50 and 100 C and pressures up to 550 bar. Predictions by Eqs. (24)-(26) agree reasonably well with the literature data [22]. Selected predictions of the bulk modulus are presented in Fig.11. Speed of sound The speed of sound in liquid DME is given by the following equation
a = E / = Z R(T + 273 )/[Z p(Z/p )T ], (27) where a is in m/s, E and p are in N/m , in kg/m , T in C, and R = 180.74 J/kg. C is the gas constant of DME. The speed of sound in liquid DME can be solved by combining Eqs. (19) and (20) and Eqs. (24)-(26) into Eq.(27). Because Z > p(Z/p )T and in the subcooledliquid region Z is more sensitive to changes in T than in p, the influence of temperature on the speed of sound is stronger than that of pressure. Figure 12 shows selected predictions of the speed of sound. Figure 13 compares predictions by Eq.(27) and the authors measurements of the speed of sound in liquid DME at 28.3 C (= 83 F) and five different pressures (12, 40, 69, 98, and 135 bar). It is seen in Fig.13 that the predictions agree well with the measurements.
2 3

900

850

800

750

Prediction by Eq.(27)
700

650

600 10

20

30

40

50

60

70

80

90

100

110

120

130

140

Pressure (bar)

Fig.13. Speed of sound in liquid DME at 28.3 C: L, measurement; , prediction by Eq.(27).

0.30

Viscosity of liquid DME (cP)

0.25

0.20

0.15

Viscosity The Morris equation [23] was selected to predict the viscosity of liquid DME because it includes the molecular-structure information. The Morris equation is given in the following: Log ( /ref) = J [400/(T + 273) 1], (28) where ref is a reference viscosity in cP (= 10 Pa.s), J = 1/2 (0.0577 + bini) , bi and ni are the contributions and the repeat numbers of the ith radical in the chemical structure, and T is in C. On the basis of the chemical formula for DME, (CH3)2O, the repeat numbers for the radical CH3 is 2 and for the radical O is 1; and, it can be determined that b = 0.0825 for the radical CH3, and b = 0.1090 for the radical O in ethers, and that the reference viscosity for ethers is ref = 0.096 cP. Substituting these values into Eq.(28) yields a viscosity equation for liquid DME:
-3

0.10

0.05 -40

-20

20

40
o

60

80

100

Temperature ( C)

Fig.14. Viscosity of liquid DME.

Thermal conductivity of liquid DME (W/m. C)

0.25

0.20

0.15

0.10

= 0.096 10 0.5759 [ 400 /(T + 273 ) 1] .

(29)

0.05 -40

-20

20

40
o

60

80

100

Temperature ( C)

At 25 C, the viscosity given by Eq.(29) is 0.151 cP. This prediction agrees with the value reported in the literature [5], = 0.150 cP. The dependence of the liquid-DME viscosity on temperature is given in Fig.14.

Fig.15 Thermal conductivity of liquid DME.

Thermal conductivity

The thermal conductivity of liquid DME may be predicted using the Robbns-Kingrea equation [23]. The R-K equation is as follows: k = (88.0 4.94H ) 10 3 220 N ) C p 4 / 3 , (30) ( * S T + 273

with

S * = H V /(T b + 273) + RLn[273 /(T + 273)],

where k is the thermal conductivity in cal/(cm.s. C), T is in C, the heat capacity Cp and gas constant R are in cal/(mol. C), the latent heat HV is in cal/mol, and the liquid density is in g/mol; N and H are chemical structure related constants. Substituting the related parameters for DME into Eq.(30), with converting all the properties into SI units, yields,

k = 6.774 10 3

4 /3 , T + 273

(31)

is a temperature effect. If the droplets are small enough, their temperature may surpass the DME critical temperature very rapidly because both the values of the latent heat and surface tension decrease with increase in temperature and become zero at the critical temperature. In this case, the DME droplets will undergo a very rapid vaporization process, as if they vaporize immediately. The second phenomenon is related to the cylinder pressure. The DME droplets in the spray may be in a subcooled liquid state initially because the pressure of the droplets is always higher than that of the ambient due to the surface tension pressure [16]. Due to combustion delay, the fuel is injected in an advance crankshaft angle before TDC. The heat release from the early-stage combustion makes the cylinder pressure increase. During this period, the pressure of the droplets increases with the cylinder pressure. When the pressure of the droplets reaches the DME critical pressure (53.7 bar), the droplets are in a supercritical state. In this case, the liquid-vapor interface disappears and the droplets may spread to the neighborhood explosively. In either of the two cases, the spray turns into a miscible turbulent jet. Glensvig et al. [26,27] and Sorenson et al. [28,29] have studied the characteristics of the DME spray. In their studies, the high-pressure liquid DME was injected into a nitrogen environment with T < 40 C and p = 15, 25, 40, and 55 bar. Thus, their tests were conducted at subcritical temperature and both subcritical and supercritical pressures. Both single-hole-nozzle and pintle-nozzle injectors were used and comparison between diesel-fuel and DME sprays under the same conditions also was conducted. Following were noticed in their investigations: (1) Vaporization of DME drops was immediately. (2) Although the penetration of the DME spray was similar to that of diesel fuel, the DMEspray developing time was much shorter than that of diesel fuel. (3) The spray angle of DME was greater than that of diesel fuel in all cases. (4) Unlike a diesel spray, the boundary of a DME spray was irregular and the irregularity increased with the cylinder pressure. At cylinder pressures near the DME critical pressure, breakup of the DME spray was noticed (which never occurs for diesel fuel). (5) Above four phenomena were similar in both cases of hole- and pintle-nozzle injectors. (6) The spray penetration and the spray angle for both diesel fuel and DME were calculated using empirical correlations. These correlations well described diesel sprays but poorly predicted patterns of DME sprays. Bek and Sorenson [30] studied the DME combustion by using a turbulent-jet model and obtained a good prediction for heat release it seems that the usual combustion delay due to the time required for vaporization of droplets in diesel-fuel sprays did not exist in the DME-spray combustion. The above experimental findings indicate that sprays of diesel fuel and DME differ significantly. The phenomena of the enlarged angle, irregular boundary, and breakup of the DME spray suggest that the DME

where the thermal conductivity k is in W/m. C and the liquid density is given by Eqs. (19) and (20). Predictions of the thermal conductivity of liquid DME agree excellently with the literature data [30] for T 80 C. The pressure range of application of Eq.(31) is p 53 bar because Eq.(24) contains information on the latent heat of DME. The dependence of the thermal conductivity of liquid-DME on temperature is given in Fig.15.
HYDRODYNAMICS OF DME SPRAY IN ENGINE CYLINDER

Being a low-boiling-point fluid, DME has a low critical temperature and a low critical pressure. Thus, the behavior of liquid DME injected into the engine cylinder is very sensitive to the cylinder temperature and pressure. Due to the surface tension (Rayleigh instability) and/or jet velocity (Weber instability), liquid DME injected into the compressed air in the cylinder breaks up into droplets. If the liquid injected breaks up completely into droplets, it is termed as a spray; otherwise, it is termed as a liquid jet [25]. From the hydrodynamic viewpoint, the difference between a spray and a miscible turbulent jet is the existence of the droplets in the spray because the droplets carry a large percent of the initial momentum of the spray. Due also to the droplets, a spray is a twophase phenomenon while a miscible turbulent jet falls into the category of the single-phase flow. The behavior of the spray is governed by sizes of the droplets and their distribution; thus, the spray characteristics, such as the spray developing time, spray angle, and penetration length, all are affected considerably by sizes of the droplets and droplet distribution. The droplet sizes in a DME spray are affected highly by the cylinder temperature and pressure. The DME spray may encounter two possible phenomena. The first

spray behave more like injection of a gaseous fluid into another gas, which is supported by Bek and Sorensons turbulent-jet combustion model [30]. As was mentioned previously, the hydrodynamic behavior of a DME spray in the engine cylinder is influenced highly by the thermodynamic state of the droplets in the spray. When the temperature and pressure fall in the subcritical region of DME, the DME spray should not show any unusual behavior in comparison to that of diesel fuel. However, when the temperature and/or pressure of the droplets enter the supercritical region of DME, the spray may behave more like a miscible turbulent jet because there is no difference between liquid and vapor in the supercritical region. In this case, a turbulent-jet model may well characterize the spray. The transition from a spray (a two-phase phenomenon) to a miscible turbulent jet (a single-phase phenomenon) may also be encountered during the spray development: if the sizes of the droplets are small enough, the droplets may completely vaporize before reaching the spray tip due to the temperature distribution in the spray. In this case, during the spray development, the dispersing droplets may dominate the spray hydrodynamics in the early stage while the air entrainment may affect considerably the later stage of the spray hydrodynamics.
SUMMARY

3. Gill, D. and Ofner, H., Dimethyl Ether A Clean Fuel for

Transportation, SAE Paper, No.990059, 1999.

4. McCandless, J.C., Teng, H. and Schneyer, J.B.,

Development of a Variable-Displacement, Rail-Pressure Supply Pump for Dimethyl Ether, SAE Paper, No.200001-0678, 2000.

5. Sorenson, S.C. and Mikkelsen, S.F., Performance and

Emissions of a 0.273 Liter Direct Injection Diesel Engine Fueled with Neat Dimethyl Ether, SAE Paper, No.950064, 1995.

6. Holldorff, H. and Knapp, H., Vapor Pressures of nButane, Dimethyl Ether, Methyl Chloride, Methanol and Vapor-Liquid Equilibrium of Dimethyl Ether-Methanol: Experimental Apparatus and Data Reduction, Fluid Phase Equilibrium, Vol.40, pp.13-25, 1988.

7. Flick, E.W., Industrial Solvents Handbook, 3rd ed., Noyes

Data Corporation, 1985.

8. Reid, R.C., Prausnitz, J.M. and Poling, B.E., The

Properties of Gases and Liquids, 4 1987.
th

ed., McGrall-Hill,

9. Hirschfelder, J.O., Curtiss, C.F. and Bird, R.D., Molecular

Theory of Gases and Liquids, John Wiley & Sons, 1954.

10. Lide, D.R., Handbook of Chemistry and Physics, 80th ed.,

CRC Press, 1999.

In this paper, the thermochemical characteristics of DME were studied. From the viewpoint of the chemical structure, the reasons that DME has a high cetane number and low emissions from combustion were analyzed. On the basis of the molecular thermodynamics of fluids, equations for commonly-used thermophysical properties of liquid DME were developed. These equations are easy to use and with engineering accuracy. Hydrodynamic characteristics of the DME spray in the engine cylinder also were analyzed. It was found that the spray behavior is influenced significantly by the thermodynamic state of the droplets in the spray. This study explained characteristics of the DME combustion reported by previous investigators.
ACKNOWLEDGMENTS

11. Masterton, W.L. and Slowinski, E.J., Chemical Principles,

W.B. Saunders Company, 1977.

12. Edgar, B., Dibble, R.W. and Naegeli, D.W., Autoignition

of Dimethyl Ether and Dimethoxy Methane Sprays at High Pressures, SAE Paper, No.971677, 1997.

13. Francisco, J.S., On the Competition between Hydrogen

Abstraction versus C-O bond Fission in Initiating Dimethyl Ether Combustion, Combustion and Flame, Vol.117, pp.312-316, 1999.

14. Fleisch, T., McCarthy, C., Basu, A., Udovich, C,

Charbonneau, P., Slodowske, W., Mikkelsen, S.-E., and McCandless, J.C., A New Clean Diesel Technology: Demonstration of ULEV Emissions on a Navistar Diesel Engine Fueled with Dimethyl Ether, SAE Paper, No.950061, 1995.

15. Challen, B. and Baranescu, R., Diesel Engine Reference The authors wish to express their gratitude to the USCAR 4SDI team, the National Renewable Energy Laboratory and the U.S. Department of Energy for their financial support of this project.
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