This is the help information for the data page on which the thermodynamic properties of the organic compounds are specified. (The data page is accessed using the "Create new compound" button on the Available Compounds page, or from the View/Edit link associated with each organic compound listed on that page.)
Here we describe each of the thermodynamic and other properties, in the order in which they appear on the data entry page. You may wish to print out this page for reference.
The first box must contain the full name of the compound, up to a maximum of 50 characters. This name will be used on the Available Compounds selection page to refer to the compound.
The second box should contain a short name for the compound, of up to 6 characters. This short name, and not the full name, will be used in the results output of the model to identify it.
Both full and short names should be unique in the current session. That is to say, two compounds selected for inclusion in a calculation cannot have the same names. This is checked by the system.
The molar mass of the compound in grams. This quantity is used to calculate the mass of the compound in the condensed phases (liquid and solid), which is shown in the results output of the model. However, the mass does not affect the equilibrium calculations carried out by the model, because all quantities in the calculation are expressed in moles.
The molar volume of the compound in cm3 per mol as a (possibly supercooled) liquid at 25 °C. This quantity is used in the estimation of the densities and volumes of liquid phase(s) in which the compound is present. If the value of the molar volume is not known – which is likely if the compound is normally a solid at room temperature – it can be estimated using the method of Girolami (1994) which is available on this website via a link on the home page.
References
G. S. Girolami (1994) J. Chem. Educ. 71, 962-964.
Use this space, up to 250 characters, for notes. They are displayed only on this page.
All inorganic compounds in the model exist in the condensed phase as solids or in aqueous solution, depending on the amount of liquid water in the system. Organic compounds have varying degrees of solubility in water, which is greatest for molecules containing polar functional groups such as -OH (alcohol) and -COOH (acid). Many compounds, for example primary hydrocarbons, are insoluble in water and are expected to form a second, hydrophobic, condensed phase which can co-exist with the aqueous phase. Some compounds may be soluble in both phases, and will partition between them.
The three buttons allow the user to define which liquid phase, or phases, the organic compound can exist in. In general, constraints should be applied if the likely behaviour of the compound is known. This simplifies calculations of the equilibrium state of the system, and makes it more likely that they will yield a satisfactory result.
The method(s) used to calculate activity coefficients of the organic compound molecule in the liquid phase(s) must also be specified, and the possible choices are presented in this section.
Activity coefficients describe the effects of non-ideality on solute and solvent behaviour in liquid mixtures. For components that can exist in the aqueous phase, three choices are possible:
1. Raoult's law. This is the simplest possible assumption, that the mole fraction activity coefficient (f(i), relative to a reference state of the pure liquid compound) of species i is equal to unity under all conditions. If Raoult's law is selected then no parameters are required and the text box will be disabled (greyed out).
2. Redlich-Kister equation. This expression (e.g., Prausnitz et al., 1986; McGlashan, 1963), with up to 10 parameters, can be used to represent solute and water activities in a pure aqueous solution over the entire concentration range from infinite dilution in water to the pure liquid solute (with no water present). Examples of the use of this equation, to represent the properties of aqueous solutions of dicarboxylic acids at 298.15 K, are given by Clegg and Seinfeld (2006). These acids are present in the public database of compounds on the Available Compounds selection page, and can be included in model calculations.
Expressions for solute (S) and water (W) mole fraction activity coefficients are given below, for terms including the first five fitted parameters (C1 to C5).
ln(fS) = ge/RT + [(1 - xS) × d(ge/RT)/d(xS)]
ln(fW) = ge/RT - [xS × d(ge/RT)/d(xS)]
where prefix x denotes mole fraction and the excess Gibbs energy per mol of substance, ge, is given by:
ge/RT = xS(1 - xS)[C1 + C2(1 - 2xS) + C3(1 - 2xS)2 + C4(1 - 2xS)3 + C5(1 - 2xS)4 ...]
and its differential with respect to xS, d(ge/RT)/d(xS), is given by:
d(ge/RT)/d(xS) = C1(1 - 2xS) + C2[-2xS(1 - xS) + (1 - 2xS)2]
+ C3[-4xS(1 - xS) + (1 - 2xS)2](1 - 2xS) + C4[-6xS(1 - xS) + (1 - 2xS)2](1 - 2xS)2
+ C5[-8xS(1 - xS) + (1 - 2xS)2](1 - 2xS)3 ...
where Ci are the fitted parameters. Both activity coefficients are relative to a reference state of the pure liquid. The logarithm of the activity coefficient of the solute can be adjusted to a reference state of infinite dilution in water (fS*) by subtracting the value obtained with the equation above for xS = 0, yielding:
ln(fS*) = ln(fS) - (ge/RT + d(ge/RT)/d(xS))
This expression is valid for any concentration but, as stated above, the final term in ge/RT and its differential is calculated for xS = 0.
The parameters of the Redlich-Kister equation should be entered, separated by spaces, in the text box. If 'n' parameters have been fitted then all of the values, including any that are zero, should be entered in the order 1 to n. For example, Clegg and Seinfeld (2006) represented the properties of aqueous malonic acid using the following 4 parameters: C1 = -0.149445, C2 = -0.403222, C3 = -0.571432, and C6 = 0.628461, see their Table 4. These would be entered in the text box as shown below.
-0.149445 -0.403222 -0.571432 0.0 0.0 0.628461
All solute activity coefficients presented in the results output of the model, for both ions and organic solutes, are relative to a reference state of infinite dilution in water.
3. Pitzer-Simonson-Clegg equation. The PSC model for multicomponent systems (Clegg et al., 1992) reduces to a two parameter expression for the case of a single solvent (here water) and uncharged solute. The expression can be used over the entire concentration range from pure water to pure liquid organic compound. Having only two parameters the equation is relatively simple, but is less flexible than the Redlich-Kister expansion described. The equations are given below for the mole fraction activity coefficients of water (fW) and the organic solute (fS):
ln(fW) = xS((1 - xW)wn,1 + (2(xW-xS)(1 - xW) + xS)(-un,1))
ln(fS) = xW((1 - xS)wn,1 + (2(xS - xW)(1 - xS) + xW)un,1)
where the fitted parameters are Wn,1 and un,1. Both activity coefficients are relative to a reference state of the pure liquid. The logarithm of the activity coefficent of the solute can be adjusted to a reference state of infinite dilution in water (fS*) by subtracting the value obtained with the equation above for xS = 0.0, xW = 1.0:
ln(fS*) = ln(fS) - (wn,1 - un,1)
All solute activity coefficients presented in the results output of the model, for both ions and organic solutes, are relative to a reference state of infinite dilution in water.
4. UNIFAC. This model (Fredenslund et al., 1975; 1977) calculates activity coefficients of mixtures of organic compounds, which may include water, in terms of the functional group composition of the molecules present. If UNIFAC is chosen from the drop-down list then the composition of the molecule, in terms of UNIFAC functional groups, must be specified in the text box. For example, the simple hydrocarbon pentane (C5H12) is composed of 2 -CH3 and 3 -CH2- groups. This would be entered in the text box as:
2*CH3 3*CH2
The order in which the groups are entered is not significant, so that the molecule could have been entered as '3*CH2 2*CH3' (without the quotes). Butanoic acid would be entered as 1*CH3 2*CH2 1*COOH. Note that the multiplier '1' must be present when the group only occurs once - so that the use of 'CH3' instead of '1*CH3' would not be valid.
All solute activity coefficients presented in the results output of the model, for both ions and organic solutes, are relative to a reference state of infinite dilution in water.
The complete list of UNIFAC functional groups available in the model is given at the end of this help page, and includes examples of how the groups are combined to make up compounds.
References
S. L. Clegg, K. S. Pitzer, and P. Brimblecombe (1992) J. Phys. Chem. 95, 9470-9479.
S. L. Clegg, and J. H. Seinfeld (2006) J. Phys. Chem. 110, 5692-5717.
Aa. Fredenslund, R. L. Jones, and J. M. Prausnitz (1975) AIChE J. 21, 1086-1098.
Aa. Fredenslund, J. Gmehling, M. L. Michelson, P. Rasmussen, and J. M. Prausnitz
(1977) Ind. Eng. Chem. Proc. Des. Dev. 16, 450-462.
M. L. McGlashan (1963) J. Chem. Educ. 40, 516-518.
J. M Prausnitz, R. N. Lichtenthaler, and E. Gomes de Azevedo (1986) Molecular Thermodynamics of
Fluid Phase Equilibria, 2nd. Edn., Prentice-Hall.
If a compound can occur in this phase, as determined by the settings made section 4 of the Organic Compound Properties page, two choices of activity coefficient expression are offered: Raoult's law, and UNIFAC. (The Redlich-Kister expression isn't included because the hydrophobic phase doesn't contain water.)
The descriptions of Raoult's law and UNIFAC below are the same as those given above for the aqueous phase. Note that, if the compound can exist in both the aqueous and the hydrophobic liquid phases, the UNIFAC group composition of the molecule can be specified in the text box for either phase.
1. Raoult's law. This is the simplest possible assumption, that the mole fraction activity coefficient (f(i), relative to a reference state of the pure liquid) of species i is equal to unity under all conditions. If Raoult's law is selected then no parameters are required and the text box will be disabled (greyed out).
2. UNIFAC. This model (Fredenslund et al., 1975; 1977) calculates activity coefficients of mixtures of organic compounds in terms of the functional group composition of the molecules present. If UNIFAC is chosen from the drop-down list then the composition of the molecule, in terms of UNIFAC functional groups, must be specified in the text box. For example, the simple hydrocarbon pentane (C5H12) is composed of 2 -CH3 and 3 -CH2- groups. This would be entered in the text box as:
2*CH3 3*CH2
The order in which the groups are entered is not significant, so that the molecule could have been entered as '3*CH2 2*CH3' (without the quotes). Butanoic acid would be entered as 1*CH3 2*CH2 1*COOH. Note that the multiplier '1' must be present when the group only occurs once - so that the use of 'CH3' instead of '1*CH3' would not be valid.
The complete list of UNIFAC functional groups available in the model (which can be found at the end of this file) includes examples of how they are combined to make up compounds.
References
Aa. Fredenslund, R. L. Jones, and J. M. Prausnitz (1975) AIChE J. 21, 1086-1098.
Aa. Fredenslund, J. Gmehling, M. L. Michelson, P. Rasmussen, and J. M. Prausnitz
(1977) Ind. Eng. Chem. Proc. Des. Dev. 16, 450-462.
Dissociation constants of organic acids, and aminium cations formed from the reactions of amines (which are organic bases) with H+, are specified in this section. If the compound is not an acid or base, or the dissociation reactions are not needed in the model, then no entry is necesssary.
For organic acids, choose "acid (single dissociation)" for a compound with one acid group (e.g., butanoic acid), or "di-acid" for one with two acid groups (e.g., succinic acid). Similarly, for amines with a single -NH2 group (e.g., methyl amine) choose "amine (single dissociation)" and for one with two groups such as methanediamine choose "di-amine".
The model is able to treat up to two dissociation equilibria. For higher acids or amines select "di-acid" or "di-amine", as appropriate, in order to enter the first two dissociation constants only.
The model is able to treat up to two dissociation equilibria of any acid so, for tricarboxylic acids, select "di-acid" in order to enter the first two dissociation constants.
The dissociation equilibrium of acid HX, or first dissociation of diacid H2Y, is defined by:
HX(aq) = H+(aq) + X−(aq),
and the molal dissociation constant Kd1 (unit: mol kg-1 of water) is:
Kd1 = aH+ · aX− / aHX, = mH+ · mX− / mHX · (γH+ · γX− / γHX)
where prefix a denotes activity, m is molality, and γ is the activity coefficient. The value of Kd1 at 298.15 K should be entered in the text box labelled "First dissociation constant".
Dissociation constants, like all equilibrium constants, vary with temperature. A box, labelled "Enthalpy change", is provided on the form for the enthalpy of dissociation ΔHo(Kd1) in units of kJ mol-1. Note the use of kJ, not J. If the enthalpy is not known then the box can be left blank and zero will be assumed, meaning that the dissociation constant will be treated as invariant with temperature.
A unique name, of up to 6 characters, should be entered for the anion X− produced by the dissociation reaction. This name will be used in the results output of the model to identify it.
The option to switch off the dissociation of each organic component is offered on the E-AIM calculation pages. Dissociation is not allowed to occur in the hydrophobic liquid phase.
Little is known about the activity coefficients of organic anions, particularly in concentrated solutions. In E-AIM the organic anions are included as additional species in the Pitzer-Simonson-Clegg model for electrolytes (Wexler and Clegg, 2002). Singly charged organic anions are assumed to have the same parameters for interactions with cations as HSO4−(aq), and doubly charged anions the same parameters as SO42−(aq). No ternary (mixture) parameters such as Wii'j and Qn,ii'j are assigned. This assumption will be most accurate in dilute solutions.
References
A. S. Wexler and S. L. Clegg (2002) J. Geophys. Res. 107, No. D14, art. no. 4207, 14 pages.
The equilibrium for the second dissociation is defined by:
H2Y(aq) = 2H+(aq) + Y2−(aq),
and the molal dissociation constant Kd2 (unit: mol2 kg-2) is:
Kd2 = (aH+)2 · aY2− / aH2Y = (mH+)2 · mY2− / mH2Y · ((γH+)2 · γY2− / γH2Y)
where prefix a denotes activity, m is molality, and γ is the activity coefficient. The value of Kd2 at 298.15 K should be entered in the text box labelled "Second dissociation constant".
Dissociation constants of di-acids and higher order acids are often tabulated in the literature as "step-wise" values. In such cases the first dissociation is as given in the previous section but the second one, for H2Y, would be defined by:
HY−(aq) = H+(aq) + Y2−(aq)
with the stepwise second dissociation constant K2 (unit: mol kg-1) given by:
K2 = aH+ · aY2− / aHY− = mH+ · mY2− / mHY− · (γH+ · γY2− / γHY)
The value of Kd2, which is the quantity that must be entered on the form, is equal to Kd1 × K2.
The enthalpy of dissociation ΔHo(Kd2) for the reaction, in units of kJ mol-1, should be entered in the text box labelled "Enthalpy change". This enthalpy is equal to the sum of the enthalpies of dissociation for the reactions for Kd1 and K2, thus ΔHo(Kd2) = ΔHo(Kd1) + ΔHo(K2). If the box is left blank the dissociation constant will be treated as invariant with temperature in the model.
A unique name, of up to 6 characters, should be entered for the divalent anion Y2− produced by the dissociation reaction. This name will be used in the results output of the model to identify it.
The option to switch off the dissociation of each organic component is offered on the E-AIM calculation pages. Dissociation is not allowed to occur in the hydrophobic liquid phase.
Little is known about the activity coefficients of organic anions, particularly in concentrated solutions. In E-AIM the organic anions are included as additional species in the Pitzer-Simonson-Clegg model for electrolytes (Wexler and Clegg, 2002. Singly charged organic anions are assumed to have the same parameters for interactions with cations as HSO4−(aq), and doubly charged anions the same parameters as SO42−(aq). No ternary (mixture) parameters such as Wii'j and Qn,ii'j are assigned. This assumption will be most accurate in dilute solutions.
References
A. S. Wexler and S. L. Clegg (2002) J. Geophys. Res. 107, No. D14, art. no. 4207, 14 pages.
The dissociation equilibrium of the amine cation RNH3+, or first dissociation of di-amine cation +H3NRNH3+, is defined by:
RNH3+(aq) = H+(aq) + RNH2(aq)
This reaction is analogous to the dissociation of the amonium cation NH4+ to yield H+ and NH3. The molal dissociation constant Kd1 (unit: mol kg-1 of water) is given by:
Kd1 = aH+ · aRNH2 / aRNH3+, = mH+ · mRNH2 / mRNH3+ · (γH+ · γRNH2 / γRNH3+)
where prefix a denotes activity, m is molality, and γ is the activity coefficient. The value of Kd1 at 298.15 K should be entered in the text box labelled "First dissociation constant".
Dissociation constants, like all equilibrium constants, vary with temperature. A box, labelled "Enthalpy change", is provided on the form for the enthalpy of dissociation ΔHo(Kd1) in units of kJ mol-1. Note the use of kJ, not J. If the enthalpy is not known then the box can be left blank and zero will be assumed, meaning that the dissociation constant will be treated as invariant with temperature.
A unique name, of up to 6 characters, should be entered for the cation RNH3+ on the left hand side of the dissociation reaction. This name will be used in the results output of the model to identify it.
The option to switch off the dissociation of each organic component is offered on the E-AIM calculation pages. Dissociation is not allowed to occur in the hydrophobic liquid phase.
Little is known about the activity coefficients of aminium cations, particularly in concentrated solutions. In E-AIM the organic cations are included as additional species in the Pitzer-Simonson-Clegg model for electrolytes (Wexler and Clegg, 2002). Singly charged organic cations are assumed to have the same parameters for interactions with anions as NH4+(aq). No ternary (mixture) parameters such as Wii'j and Qn,ii'j are assigned. This assumption will be most accurate in dilute solutions, and for relatively small aminium cations.
References
A. S. Wexler and S. L. Clegg (2002) J. Geophys. Res. 107, No. D14, art. no. 4207, 14 pages.
X. Ge, A. S. Wexler and S. L. Clegg (2011) Atmos. Environ. 45, 561-577.
The equilibrium for the second dissociation is defined by:
+H3NRNH3+(aq) = 2H+(aq) + H2NRNH2(aq),
and the molal dissociation constant Kd2 (unit: mol2 kg-2) is:
Kd2 = (aH+)2 · aH2NRNH2 / a(+H3NRNH3+)
= (mH+)2 · mH2NRNH2 / m(+H3NRNH3+) · ((γH+)2 · γH2NRNH2 / γ(+H3NRNH3+))
where prefix a denotes activity, m is molality, and γ is the activity coefficient. The value of Kd2 at 298.15 K should be entered in the text box labelled "Second dissociation constant".
Dissociation constants of di-amines and higher order amines are often tabulated in the literature as "step-wise" values. In such cases the first dissociation is as given in the previous section but the second one for H2NRNH2+ would be defined by:
+H3NRNH3+(aq) = H+(aq) + H2NRNH3+(aq)
with the stepwise second dissociation constant K2 (unit: mol kg-1) given by:
K2 = aH+ · aH2NRNH3+ / a(+H3NRNH3+)
= mH+ · mH2NRNH3+ / mHY− · (γH+ · γH2NRNH3+ / γ(+H3NRNH3+))
The value of Kd2, which is the quantity that must be entered on the form, is equal to Kd1 × K2.
The enthalpy of dissociation ΔHo(Kd2) for the reaction, in units of kJ mol-1, should be entered in the text box labelled "Enthalpy change". This enthalpy is equal to the sum of the enthalpies of dissociation for the reactions for Kd1 and K2, thus ΔHo(Kd2) = ΔHo(Kd1) + ΔHo(K2). If the box is left blank the dissociation constant will be treated as invariant with temperature in the model.
A unique name, of up to 6 characters, should be entered for the divalent cation (+H3NRNH3+) produced by the dissociation reaction. This name will be used in the results output of the model to identify it.
The option to switch off the dissociation of each organic component is offered on the E-AIM calculation pages. Dissociation is not allowed to occur in the hydrophobic liquid phase.
Little is known about the activity coefficients of organic cations, particularly in concentrated solutions. In E-AIM the organic ions are included as additional species in the Pitzer-Simonson-Clegg model for electrolytes (Wexler and Clegg, 2002. Doubly charged organic cations are assumed to obey the Debye-Huckel limiting law, and all specific interaction parameters that include the cations are set to zero. No ternary (mixture) parameters such as Wii'j and Qn,ii'j are assigned. These assumptions will be most accurate in very dilute solutions.
References
A. S. Wexler and S. L. Clegg (2002) J. Geophys. Res. 107, No. D14, art. no. 4207, 14 pages.
X. Ge, A. S. Wexler and S. L. Clegg (2011) Atmos. Environ. 45, 561-577.
The contribution of the dissolved organic compound to the surface tension of the aqueous phase, or hydrophobic organic liquid phase, can be specified in terms of up to six parameters of the surface tension model of Dutcher et al. (2010): aws, bws, asw, bsw, c1 and c2. The units used are mN m-1. Generally only one or two of these parameters will be used. The reference should be consulted for a full description. However, if only the surface tension of the liquid organic compound at 25 °C is known, then this can be entered in the box for c1.
If no values are entered the compound will be assumed to have no effect on the surface tension of the aqueous solution or liquid mixture. Note that the surface tension model used in E-AIM applies to electrolytes and uncharged solutes dissolved in bulk solutions and mixtures, and not to the "surface active" compounds can concentrate at the solution and droplet surfaces and have a very large effect on surface tension.
References
C. S. Dutcher, A. S. Wexler and S. L. Clegg (2010) J. Phys. Chem. A, 114, 12216-12230.
The equilibrium vapour pressures of organic compounds range over many orders of magnitude. Very large molecules, for example, may have vapour pressures so low that they will be found only in the condensed phase. For such molecules select 'involatile' (the default).
The volatility of other organic compounds, which partition between the condensed and gas phases, can be specified in two different ways: first, as a Henry's law constant that describes the equilibrium between the compound in the gas phase and in aqueous solution. Second, as the vapour pressure of the pure liquid compound. This vapour pressure, for 298.15 K, should be a value for the supercooled liquid if the normal melting point is above this temperature. Select the radio button for the constant that will be entered.
The molal Henry's law constant KH (unit: mol kg-1 atm-1) describes the following equilibrium between the compound 'Org' in the gas phase and in aqueous solution:
Org(g) = Org(aq)
for which KH is defined by:
KH = aOrg / pOrg = mOrg · γOrg / pOrg
where prefix a denotes activity, p denotes partial pressure (in atmospheres), m is molality, and γ is the molal activity coefficient. The value of KH at 298.15 K should be entered in the text box labelled Henry's law constant.
Henry's law constants vary with temperature, typically increasing by a factor of about 2 for every 10 K reduction in temperature. A box is provided for the enthalpy change ΔHo(KH) (unit: kJ mol-1) associated with the Henry's law reaction at 298.15 K. Note the use of kJ, not J. A further text box is also provided for the heat capacity change ΔCpo(KH) (unit: J mol-1 K-1) for the Henry's law reaction. The heat capacity change describes the variation of the enthalpy change with temperature, and has a significant influence on the value of KH for temperatures far from 298.15 K.
If the enthalpy and heat capacity values are not known then the boxes can be left blank and zeros will be assumed, meaning that the Henry's law constant will be treated as invariant with temperature.
Volatility can also be expressed in terms of the vapour pressure po (in atmospheres) of the organic compound at 298.15 K, together with an associated enthalpy of vaporisation ΔHo(po) (in kJ mol-1) and heat capacity change ΔCpo(po) (in J mol-1 K-1). The vapour pressure should be the value for the pure liquid compound at 298.15 K, which will be a 'sub-cooled' vapour pressure for compounds that have a normal melting point above room temperature.
Text boxes are provided in which po can be entered, together with ΔHo(po) and ΔCpo(po) if known. If the enthalpy and heat capacity are not known then the boxes can be left blank and zeros will be assumed, meaning that the vapour pressure will be treated as invariant with temperature.
Users should be aware that the Henry's law constant and sub-cooled liquid vapour pressure are related by the equation:
po = 1 / [KH(x) · f(inf. dil.)]
where KH(x) is the Henry's law constant on the mole fraction concentration scale (unit: atm-1), and f(inf. dil.) is the mole fraction based activity coefficient of the organic compound at infinite dilution in water, relative to a reference state of the pure liquid compound (i.e., for which f → 1.0 as the mole fraction x of the organic compound tends to unity.)
Values of po entered on this page are converted internally to KH(x), using f(inf. dil.) calculated with the activity coefficient expression entered on section 4 of the form, and then to Gibbs energies of formation. Thermal quantities ΔHo(po) and ΔCpo(po) are converted similarly, according to:
ΔHo(KH(x)) = - [ΔHo(po) + RTr2 · d(ln f(inf. dil.))/dT]
ΔCpo(KH(x)) = - [ΔCpo(po) + 2RTr · d(ln f(inf. dil.))/dT + RTr2 · d2(ln f(inf. dil.))/dT2]
where R (8.3144 J mol-1 K-1) is the gas constant, Tr is the reference temperature of 298.15 K, and the final terms on the right hand side of both equations are differentials of the natural logarithm of f(inf. dil.) with respect to temperature.
It is clear from these equations that the two alternative ways of specifying volatility - Henry's law constant or the vapour pressure of the pure liquid - will only yield the same results in model calculations if the two quantities and the activity coefficient model are consistent so that the above equations are satisfied.
Water soluble organic compounds, such as dicarboxlylic acids, can form solids from saturated solutions. These solids may be anhydrous (containing no water), or may be hydrates. For example the equilibrium solid form of oxalic acid at 298.15 K is the dihydrate (COOH)2.2H2O(s).
Select "simple solid" if the solid is anhydrous, or "solid hydrate" if it contains water.
For solid hydrates, enter the number of water molecules in the formula of the solid, for example "2" for the solid oxalic acid dihydrate. If zero is entered, or the field is left blank, the solid will be treated as anhydrous (i.e., a simple solid with no water present).
The equilibrium between aqueous solutions containing an organic compound Org, and the organic solid or its hydrate, is described by:
Org(aq) + nH2O(s) = Org.nH2O(s)
where n, which is greater than or equal to zero, is the number of water molecules. The molal solubility product Ks (unit: mol kg-1) is given by:
Ks = aOrg · aH2On = mOrg · γOrg · aH2On
where prefix a denotes activity, m is molality, γOrg is the molal activity coefficient of Org, and aH2O is the water activity. (The activity of a pure solid is unity by definition, and so does not appear in the equation.) Enter a value for Ks at 298.15 K in the text box labelled "Activity product in saturated solution".
Solid solubilities, and consequently Ks, vary with temperature. This is described within the model by the enthalpy change ΔHo(Ks) (unit: kJ mol-1), and the heat capacity change ΔCpo(Ks) (unit: J mol-1 K-1) for the reaction. Note the use of kJ, and not J, for the enthalpy. Enter values of the two quantities at 298.15 K, if known, in the boxes provided. If no entries are made then zeros will be assumed, meaning that Ks will be treated as invariant with temperature.
If the "Keep for current session only" option is selected then information entered on the page - modifications to the properties of existing compounds in the library or data for newly created compounds - will be lost when the browser is closed and the session ends. If you are not logged in (which requires registration) this is the only option that is offered.
If you have logged in you can also save the data to your private library. This is retained on the E-AIM server and all compounds in your library will be available to you when you next log in, and will be added to the drop-down list on the Available Compounds page. Checking the "make compound public" box will allow other people to use this compound, and any others you make public in this way, if you tell them your library code. Other users are not able to change the properties of the public compounds in your database, though they can make temporary alterations by saving the editied compound(s) to their session.
Note that, when you save data to a library either for a new compound or by overwriting an existing one, the thermodynamic property data in the session is not updated. This must be done separately.
The facility of making compounds public is useful if you teach a class and want to allow students to do calculations using a set of compounds that you have defined. These can be made public, for use by the class, while other compounds in the library - which you might use for research - are kept hidden.
The information entered on the properties page becomes available for use in calculations when the "Keep for current session only" radio button is selected and the contents of the form are saved by pressing the button "Save the data". When this is done the information on the form is checked for validity, and any errors identified and marked for correction. If all the tests are passed, the properties of the compound entered on the form will be stored and the user returned to the Available Compounds page.
If you are logged in and choose to save the compound a library instead of the current session, you will need to select it from the drop down box on the Available Compounds page in order to include it in E-AIM calculations.
Similarly, if you overwrite an existing compound in your library the version in the session (listed on the Available Compounds page) is not changed. In order to use the new definition from the library you should remove the session copy by clicking the link provided, and then reselect the compound from the library.
Keep in mind this important distinction: organic compounds and properties which are present in the session are used in the E-AIMthermodynamic calculations. These are the compounds that are listed on the Available Compounds page, together with "Remove" and "View/Edit" buttons. All of the session information is lost when you close your browser, or log out. The organic compounds present in the libraries, which are listed in the drop down selection box on the Available Compounds page, are stored permanently in a database. You save data from this page either to the session or to a library (this option is available only if you log in), not to both simultaneously.
For the standard UNIFAC parameter set implemented in the model the sources of values are:
H. K. Hansen, P. Rasmussen, A. Fredenslund, M. Schiller, and J Gmehling (1991) Ind. Eng. Chem. Res. 30, 2352-2355.
R. Wittig, J. Lohmann, and J. Gmehling (2003) Ind. Eng. Chem. Res. 42, 183-188.
We have also added functional groups and parameters from:
K. Balslev and J. Abildskov (2002) Ind. Eng. Chem. Res. 41, 2047-205.
In the parameter set modified by C. K. Chan and co-workers (C. Peng, M. N. Chan, and C. K. Chan (2001) Environ. Sci. Technol. 35, 4495-4501) the following changes are made to values of interaction parameters a(i,j):
Sub
Groups Peng Standard
i j a(i,j) a(i,j)
---- ---- ----- ------
OH COOH 224.39 199.0
COOH OH -103.03 -151.0
OH H2O 265.87 353.5
H2O OH -467.42 -229.1
H2O COOH -69.29 -14.09
COOH H2O -145.88 66.17
In Table 1 below the symbol for each functional group is listed together with the main group number in the first column, the fitted parameters Rk and Qk, and examples of how the groups are used to specify molecular group composition in the model.
Values of the parameters a(i,j) and a(j,i) for main group interactions are listed after the table.
Table 1. UNIFAC Structural Groups and Examples of Their Use
Group Symbol Rk Qk Example
-----------------------------------------------------------------
1 alkane group
-------------------
CH3 (end group of chain) 0.9011 0.848 ethane: 2*CH3
CH2 (middle group of chain) 0.6744 0.540 n-butane: 2*CH3 2*CH2
CH (middle group of chain) 0.4469 0.228 isobutane: 3*CH3 1*CH
C (bonded to 4 other C) 0.2195 0.0 neopentane: 4*CH3 1*C
2 alpha-olefin group
-------------------------
CH2=CH 1.3454 1.176 hexene-1: 1*CH3 3*CH2 1*CH2=CH
CH=CH 1.1167 0.867 hexene-2: 1*CH3 2*CH2 1*CH=CH
CH2=C 1.1173 0.988 2-methyl-1-butene: 2*CH3 1*CH2 1*CH2=CH
CH=C 0.8886 0.676 2-methyl-2-butene: 2*CH3 1*CH=C
C=C 0.6605 0.485 2,3-dimethylbutene: 4*CH3 1*C=C
3 aromatic carbon
----------------------
ACH 0.5313 0.400 napthaline: 8*ACH 2*AC
AC 0.3652 0.120 styrene: 1*CH2=CH 5*ACH 1*AC
4 aromatic carbon-alkane
-----------------------------
ACCH3 1.2663 0.968 toluene: 5*ACH 1*ACCH3
ACCH2 1.0396 0.660 ethylbenzene: 5*ACH 1*ACCH2 1*CH3
ACCH 0.8121 0.348 cumene: 2*CH3 5*ACH 1*ACCH
5 alcohol
--------------
OH 1.0000 1.200 propanol-2: 2*CH3 1*CH 1*OH
methanol
---------------
6 CH3OH 1.4311 1.432 methanol: 1*CH3OH
7 water
------------
H2O 0.92 1.4 water: 1*H2O
8 aromatic carbon-alcohol
-----------------------------
ACOH 0.8952 0.68 phenol: 5*ACH 1*ACOH
9 carbonyl
---------------
CH3CO 1.6724 1.448 butanone: 1*CH3 1*CH2 1*CH3CO
CH2CO 1.4457 1.180 pentanone-3: 2*CH3 1*CH2 1*CH2CO
10 aldehyde
---------------
HCO 0.9980 0.948 propionaldehyde: 1*CH3 1*CH2 1*CHO
11 acetate group
--------------------
CH3COO 1.9031 1.728 butyl acetate: 1*CH3 3*CH2 1*CH3COO
CH2COO 1.6764 1.420 methyl propionate: 2*CH3 1*CH2COO
12 formate group
--------------------
HCOO 1.2420 1.188 ethyl formate: 1*CH3 1*CH2 1*HCOO
13 ether
------------
CH3O 1.1450 1.088 dimethyl ether: 1*CH3 1*CH3CO
CH2O 0.9183 0.780 diethyl ether: 2*CH3 1*CH2 1*CH2O
CHO 0.6908 0.468 diisopropyl ether: 4*CH3 1*CH 1*CHO
THF 0.9183 1.100 tetrahydrofuran: 3*CH2 1*THF
14 primary amine
-------------------
CH3NH2 1.5959 1.544 methylamine: 1*CH3NH2
CH2NH2 1.3692 1.236 ethylamine 1*CH3 1*CH2NH2
CHNH2 1.1417 0.924 isopropyl amine: 2*CH3 1*CHNH2
15 secondary amine group
----------------------------
CH3NH 1.4337 1.244 dimethylamine: 1*CH3 1*CH3NH
CH2NH 1.2070 0.936 diethylamine: 2*CH3 1*CH2 1*CH2NH
CHNH 0.9795 0.624 diisopropyl amine: 4*CH2 1*CH 1*CHNH
16 tertiary amine
---------------------
CH3N 1.1865 0.940 trimethylamine: 2*CH3 1*CH3N
CH2N 0.9597 0.632 triethylamine: 3*CH3 2*CH2 1*CH2N
17 aromatic amine
---------------------
ACNH2 1.0600 0.816 aniline: 5*ACH 1*ACNH2
18 pyridine
---------------
C5H5N 2.9993 2.113 pyridine: 1*C5H5N
C5H4N 2.8332 1.833 2-methylpyridine: 1*CH3 1*C5H4N
C5H3N 2.6670 1.553 2 3-dimethylpyridine: 2*CH3 1*C5H3N
19 CCN
----------
CH3CN 1.8701 1.724 acetonitrile: 1*CH3CN
CH2CN 1.6434 1.416 propionitrile: 1*CH3 1*CH2CN
20 COOH
-----------
COOH 1.3013 1.224 acetic acid: 1*CH3 1*COOH
HCOOH 1.5280 1.532 formic acid: 1*HCOOH
21 CCl
----------
CH2Cl 1.4654 1.264 butane-1-chloro: 1*CH3 2*CH2 1*CH2Cl
CHCl 1.2380 0.952 propane-2-chloro: 2*CH3 1*CHCl
CCl 1.0106 0.724 2-methylpropane-2-chloro: 2*CH3 1*CCl
22 CCl2
-----------
CH2Cl2 2.2564 1.998 methane-dichloro: 1*CH2Cl2
CHCl2 2.0606 1.684 ethane-1,1-dichloro: 1*CH3 1*CHCl2
CCl2 1.8016 1.448 propane-2,2-dichloro: 2*CH3 1*CCl2
23 CCl3
-----------
CHCl3 2.8700 2.410 chloroform: 1*CHCl3
CCl3 2.6401 2.184 ethane-1,1,1-trichloro: 1*CH3 1*CCl3
24 CCl4
-----------
CCl4 3.3900 2.910 methane-tetrachloro: 1*CCl4
25 aromatic chloro
---------------------
ACCl 1.1562 0.844 benzene-chloro: 5*ACH 1*ACCl
26 CNO2
-----------
CH3NO2 2.0086 1.868 nitromethane: 1*CH3NO2
CH2NO2 1.7818 1.560 propane-1-nitro: 1*CH3 1*CH2 1*CH2NO2
CHNO2 1.5544 1.248 propane-2-nitro: 2*CH3 1*CHNO2
27 aromatic nitro
---------------------
ACNO2 1.4199 1.104 benzene-nitro: 5*ACH 1*ACNO2
28 carbon disulphide
------------------------
CS2 2.0570 1.650 carbon disulphide: 1*CS2
29 CH3SH
------------
CH3SH 1.8770 1.676 methanethiol: 1*CH3SH
CH2SH 1.6510 1.368 ethanethiol: 1*CH3 1*CH2SH
30 furfural
---------------
furfural 3.1680 2.484 furfural: 1*furfural
31 ethanediol
-----------------
DOH 2.4088 2.248 1,2-ethanediol: 1*DOH
32 iodo compounds
---------------------
I 1.2640 0.992 iodoethane: 1*CH3 1*CH2 1*I
33 bromo compounds
----------------------
Br 0.9492 0.832 bromoethane: 1*CH3 1*CH2 1*Br
34 carbon triple bond
-------------------------
CH{triple}C 1.2920 1.088 hexyne-1: 1*CH3 3*CH2 1*CH{triple}C
C{triple}C 1.0613 0.784 hexyne-2: 2*CH3 2*CH2 1*C{triple}C
35 dimethylsulphoxide
-------------------------
DMSO 2.8266 2.472 dimethylsulfoxide: 1*DMSO
36 acrylonitrile
--------------------
acrylnitrile 2.3144 2.052 acrylnitrile: 1*acrylnitrile
37 Cl, double bonded carbon
-------------------------------
Cl-C=C 0.7910 0.724 ethene-trichloro: 1*CH=C 3*Cl-(C=C)
38 aromatic fluoro
----------------------
ACF 0.6948 0.524 hexafluorobenzene: 6*ACF
39 DMF
----------
DMF 3.0856 2.736 n,n-dimethylformamide: 1*DMF
HCON(CH2)2 2.6322 2.120 n,n-diethylformamide: 2*CH3 1*HCON(CH2)2
40 CF2
----------
CF3 1.4060 1.380 perfluorohexane: 2*CF3 4*CF2
CF2 1.0105 0.920
CF 0.6150 0.460 perfluoromethylcyclohexane: 1*CF3 5*CF2 1*CF
41 acrylate
---------------
COO 1.3800 1.200 methyl acrylate: 1*CH3 1*CH2=CH 1*COO
42 SiH2
-----------
SiH3 1.6035 1.263 methylsilane: 1*CH3 1*SiH3
SiH2 1.4443 1.006 diethylsilane: 2*CH3 2*CH2 1*SiH2
SiH 1.2853 0.749 heptamethyltrisiloxane: 7*CH3 2*SiO 1*SiH
Si 1.0470 0.410 heptamethyldisiloxane: 6*CH3 1*SiO 1*Si
43 SiO
----------
SiH2O 1.4838 1.062 1,3-dimethyldisiloxane: 3*CH3 1*SiH2O 1*SiH2
SiHO 1.3030 0.764 1,1,3,3-tetramethyldisiloxane: 4*CH3 1*SiHO 1*SiH
SiO 1.1044 0.466 octamethylcyclotetrasiloxane: 8*CH3 4*SiO
44 methylpyrrolidone
------------------------
NMP 3.9810 3.200 n-methylpyrrolidone: 1*NMP
45 CClF
-----------
CCl3F 3.0356 2.644 trichlorofluoromethane: 1*CCl3F
CCl2F 2.2287 1.916 tetrachloro-1,2-difluoroethane: 2*CCl2F
HCCl2F 2.4060 2.116 dichlorofluoromethane: 1*HCCl2F
HCClF 1.6493 1.416 1-chloro-1,2,2,2-tetrafluoroethane: 1*CF3 1*HCClF
CClF2 1.8174 1.648 1,2-dichlorotetrafluoroethane: 2*CClF2
HCClF2 1.9670 1.828 chlorodifluoromethane: 1*HCClF2
CClF3 2.1721 2.100 chlorotrifluoromethane: 1*CClF3
CCl2F2 2.6243 2.376 dichlorodifluoromethane: 1*CCl2F2
46 CON
----------
CONH2 1.4515 1.248 acetamide: 1*CH3 1*CONH2
CONHCH3 2.1905 1.796 n-methylacetamide: 1*CH3 1*CONHCH3
CONHCH2 1.9637 1.488 n-ethylacetamide: 2*CH3 1*CONHCH2
CON(CH3)2 2.8589 2.428 n,n-dimethylacetamid: 1*CH3 1*CON(CH3)2
CONCH3CH2 2.6322 2.120 n,n-methylethylacetamid: 2*CH3 1*CONCH3CH2
CON(CH2)2 2.4054 1.812 n,n-diethylacetamid: 3*CH3 1*CON(CH2)2
47 OCCOH
------------
C2H5O2 2.1226 1.904 2-ethoxyethanol: 1*CH3 1*CH2 1*C2H5O2
C2H4O2 1.8952 1.592 2-ethoxy-1-propanol: 2*CH3 1*CH2 1*C2H4O2
48 CH2S
-----------
CH3S 1.6130 1.368 dimethylsulphide: 1*CH3 1*CH3S
CH2S 1.3863 1.060 diethylsulphide: 2*CH3 1*CH2 1*CH2S
CHS 1.1589 0.748 diisopropylsulphide: 4*CH3 1*CH 1*CHS
49 morpholine
-----------------
morpholine 3.4740 2.796 morpholine: 1*MORPH
50 thiophene
----------------
C4H4S 2.8569 2.140 thiophene: 1*C4H4S
C4H3S 2.6908 1.860 2-methylthiophene: 1*CH3 1*C4H3S
C4H2S 2.5247 1.580 2 3-dimethylthiophene: 2*CH3 1*C4H2S
52 sulphones
----------------
CH2SuCH2 2.6869 2.120 sulfolane: 1*CH2SuCH2 2*CH3
CH2SuCH 2.4595 1.808 2,4 dimethyl sulfolane: 1*CH2SuCH 1*CH3 1*CH2 1*CH
53 oxides
-------------
CH2OCH2 1.5926 1.320 ethylene oxide: 1*CH2OCH2
CH2OCH 1.3652 1.008 1,2-propylene oxied: 1*CH3 1*CH2OCH
CH2OC 1.1378 0.780 1,2-epoxy-2-methylpropane: 2*CH3 1*CH2OC
CHOCH 1.1378 0.696 2,3 epoxybutane: 2*CH3 1*CHOCH
CHOC 0.9103 0.468 2,3-epoxy-2-methylbutane: 3*CH3 1*CHOCH
COC 0.6829 0.240 2,3-epoxy-2 3-dimethylbutane: 4*CH3 1*COC
54 anhydrides
-----------------
O=COC=O 1.7732 1.520 acetic anhydride: 2*CH3 1*O=COC=O
55 aromatic nitrile
-----------------------
AC-CN 1.3342 0.996 benzonitrile: 5*ACH 1*AC-CN
56 aromatic bromo
---------------------
AC-Br 1.3629 0.972 bromobenzene: 5*ACH 1*AC-Br
The UNIFAC energy interaction parameters are listed in Table 2 below. Each sub group (for example, the CH3, CH2, CH and C listed for the main group 'alkanes') has the same set of energy interaction parameters. These parameters are referenced by main group number (column 1 from Table 1).
Table 2. UNIFAC Energy Interaction Parameters
i j a(i,j) i j a(i,j) i j a(i,j) i j a(i,j) i j a(i,j)
--------------- --------------- --------------- --------------- -----------
1 1 0.0000 1 7 1318.0 1 16 206.60 11 25 442.40 1 39 485.30
2 1 -35.360 2 7 270.60 2 16 61.110 12 25 24.280 2 39 -70.450
3 1 -11.120 3 7 903.80 3 16 90.490 13 25 134.80 3 39 245.60
4 1 -69.700 4 7 5695.0 4 16 23.500 14 25 30.050 4 39 5629.0
5 1 156.40 5 7 353.50 5 16 -323.00 15 25 -18.930 5 39 -143.90
6 1 16.510 6 7 -181.00 6 16 53.900 16 25 -181.90 6 39 -172.40
7 1 300.00 7 7 0.0000 7 16 304.00 17 25 617.50 7 39 319.00
8 1 275.80 8 7 -601.80 9 16 -169.00 18 25 -2.17 9 39 -61.700
9 1 26.76 9 7 472.50 11 16 -196.70 19 25 -4.6240 10 39 -268.80
10 1 505.70 10 7 480.80 13 16 5422.3 20 25 -79.080 11 39 85.330
11 1 114.80 11 7 200.80 14 16 -41.110 21 25 153.00 12 39 308.90
12 1 329.30 12 7 124.63 15 16 -189.20 22 25 223.10 13 39 254.80
13 1 83.360 13 7 -314.70 16 16 0.0000 23 25 192.10 14 39 -164.00
14 1 -30.480 14 7 -330.48 17 16 -24.46 24 25 -75.970 15 39 -255.22
15 1 65.330 15 7 -448.20 19 16 -446.86 25 25 0.0000 16 39 22.050
16 1 -83.980 16 7 -598.80 21 16 151.38 26 25 132.90 17 39 -334.40
17 1 1139.0 17 7 -341.60 22 16 -141.40 27 25 -123.10 19 39 -151.50
18 1 -101.60 18 7 -332.90 23 16 -293.70 33 25 -185.30 20 39 -228.00
19 1 24.820 19 7 242.80 24 16 316.90 35 25 -334.12 21 39 6.57
20 1 315.30 20 7 -66.170 25 16 2951.0 39 25 -374.16 22 39 -160.28
21 1 91.460 21 7 698.20 35 16 -257.2 40 25 33.95 24 39 498.60
22 1 34.010 22 7 708.70 38 16 116.50 41 25 1107.0 25 39 5143.14
23 1 36.700 23 7 826.76 39 16 -185.20 44 25 161.50 26 39 -223.10
24 1 -78.450 24 7 1201.0 1 17 920.70 47 25 7.0820 29 39 78.920
25 1 106.80 25 7 -274.50 2 17 749.30 1 26 661.50 31 39 302.20
26 1 -32.690 26 7 417.90 3 17 648.20 2 26 357.50 33 39 336.25
27 1 5541.0 27 7 360.70 4 17 664.20 3 26 168.00 34 39 -119.80
28 1 -52.650 28 7 1081.0 5 17 -52.390 4 26 3629.0 35 39 -97.710
29 1 -7.4810 30 7 23.480 6 17 489.70 5 26 256.50 36 39 -8.8040
30 1 -25.310 31 7 -137.40 7 17 459.00 6 26 75.140 37 39 255.00
31 1 140.00 33 7 79.18 8 17 -305.50 7 26 220.60 38 39 -110.65
32 1 128.00 35 7 -240.00 9 17 6201.0 9 26 137.50 39 39 0.0000
33 1 -31.520 36 7 386.60 11 17 475.50 11 26 -81.130 40 39 55.800
34 1 -72.880 39 7 -287.10 13 17 -46.39 13 26 95.180 41 39 -28.650
35 1 50.490 41 7 284.40 14 17 -200.70 19 26 -0.5150 1 40 -2.8590
36 1 -165.90 42 7 180.20 15 17 138.54 21 26 32.730 2 40 449.40
37 1 47.410 44 7 832.20 16 17 287.43 22 26 108.90 3 40 22.670
38 1 -5.1320 46 7 -509.30 17 17 0.0000 24 26 490.90 4 40 -245.39
39 1 -31.950 47 7 -205.70 18 17 117.40 25 26 132.70 13 40 -172.51
40 1 147.30 49 7 -384.30 19 17 777.40 26 26 0.0000 25 40 309.58
41 1 529.00 52 7 627.39 20 17 493.80 27 26 -85.120 38 40 -117.20
42 1 -34.360 1 8 1333.0 21 17 429.70 28 26 277.80 39 40 -5.5790
43 1 110.20 2 8 526.10 22 17 140.80 31 26 481.30 40 40 0.0000
44 1 13.890 3 8 1329.0 24 17 898.20 32 26 64.280 45 40 -32.170
45 1 30.740 4 8 884.90 25 17 334.90 33 26 125.30 1 41 387.10
46 1 27.970 5 8 -259.70 27 17 134.90 34 26 174.40 2 41 48.330
47 1 -11.920 6 8 -101.70 31 17 192.30 37 26 379.40 3 41 103.50
48 1 39.930 7 8 324.50 39 17 343.70 39 26 223.60 4 41 69.260
49 1 -23.610 8 8 0.0000 41 17 -22.100 41 26 -124.70 5 41 190.30
50 1 -8.4790 9 8 -133.1 1 18 287.77 45 26 844.00 6 41 165.70
52 1 245.21 10 8 -155.60 2 18 280.50 50 26 176.30 7 41 -197.50
1 2 86.020 11 8 -36.720 3 18 -4.4490 1 27 543.00 8 41 -494.20
2 2 0.0000 12 8 -234.25 4 18 52.800 3 27 194.90 9 41 -18.800
3 2 3.4460 13 8 -178.5 5 18 170.00 4 27 4448.0 10 41 -275.50
4 2 -113.60 14 8 -870.8 6 18 580.50 5 27 157.10 11 41 560.20
5 2 457.00 17 8 -253.10 7 18 459.00 6 27 457.88 12 41 -70.240
6 2 -12.520 18 8 -341.60 8 18 -305.50 7 27 399.50 13 41 417.00
7 2 496.10 20 8 -11.000 9 18 7.3410 8 27 -413.48 15 41 -38.770
8 2 217.50 22 8 1633.5 11 18 -0.13 9 27 548.50 17 41 -89.420
9 2 42.920 24 8 10000 12 18 -233.40 13 27 155.11 19 41 120.30
10 2 56.300 25 8 622.30 13 18 213.20 17 27 -139.30 20 41 -337.00
11 2 132.10 27 8 815.12 15 18 431.49 18 27 2845.0 21 41 63.670
12 2 110.40 28 8 1421.0 17 18 89.700 21 27 86.200 22 41 -96.870
13 2 26.510 31 8 838.40 18 18 0.0000 24 27 534.70 23 41 255.80
14 2 1.1630 41 8 -167.30 19 18 134.30 25 27 2213.0 24 41 256.50
15 2 -28.700 44 8 -234.70 20 18 -313.50 26 27 533.20 25 41 -145.10
16 2 -25.380 50 8 810.50 22 18 587.30 27 27 0.0000 26 41 248.40
17 2 2000.0 1 9 476.40 23 18 18.980 32 27 2448.0 28 41 469.80
18 2 -47.630 2 9 182.60 24 18 368.50 33 27 4288.0 30 41 43.370
19 2 -40.620 3 9 25.770 25 18 20.18 1 28 153.60 31 41 347.80
20 2 1264.0 4 9 -52.100 27 18 2475.0 2 28 76.302 32 41 68.550
21 2 40.250 5 9 84.000 33 18 -42.710 3 28 52.070 33 41 -195.10
22 2 -23.500 6 9 23.390 37 18 281.60 4 28 -9.4510 35 41 153.70
23 2 51.060 7 9 -195.40 38 18 159.80 5 28 488.90 36 41 423.40
24 2 160.90 8 9 -356.10 50 18 221.40 6 28 -31.090 37 41 730.80
25 2 70.320 9 9 0.0000 1 19 597.00 7 28 887.10 39 41 72.310
26 2 -1.9960 10 9 128.00 2 19 336.90 8 28 8484.0 41 41 0.0000
28 2 16.620 11 9 372.20 3 19 212.50 9 28 216.10 47 41 101.2
30 2 82.640 12 9 385.40 4 19 6096.0 11 28 183.00 1 42 -450.40
33 2 174.60 13 9 191.10 5 19 6.7120 13 28 140.90 3 42 -432.30
34 2 41.380 15 9 394.60 6 19 53.280 19 28 230.90 4 42 683.30
35 2 64.070 16 9 225.30 7 19 112.60 21 28 450.10 5 42 -817.70
36 2 573.00 17 9 -450.30 9 19 481.70 23 28 116.60 7 42 -363.80
37 2 124.20 18 9 29.100 10 19 -106.4 24 28 132.20 9 42 -588.90
38 2 -131.70 19 9 -287.50 11 19 494.60 26 28 320.20 13 42 1338.0
39 2 249.00 20 9 -297.80 12 19 -47.250 28 28 0.0000 14 42 -664.40
40 2 62.400 21 9 286.30 13 19 -18.510 32 28 -27.450 15 42 448.10
41 2 1397.0 22 9 82.860 14 19 358.90 37 28 167.90 20 42 169.30
44 2 -16.110 23 9 552.10 15 19 147.10 41 28 885.50 42 42 0.0000
46 2 9.7550 24 9 372.00 16 19 1255.10 1 29 184.40 43 42 745.30
47 2 132.40 25 9 518.40 17 19 -281.60 3 29 -10.430 1 43 252.70
48 2 543.60 26 9 -142.60 18 19 -169.70 4 29 393.60 3 43 238.90
49 2 161.10 27 9 -101.50 19 19 0.0000 5 29 147.50 4 43 355.50
52 2 384.45 28 9 303.70 20 19 92.07 6 29 17.500 5 43 202.70
1 3 61.130 29 9 160.60 21 19 54.320 9 29 -46.280 14 43 275.90
2 3 38.810 30 9 317.50 22 19 258.60 12 29 103.90 15 43 -1327.0
3 3 0.0000 31 9 135.40 23 19 74.040 13 29 -8.5380 20 43 127.20
4 3 -146.80 32 9 138.00 24 19 492.00 14 29 -70.140 24 43 233.10
5 3 89.600 33 9 -142.60 25 19 363.50 19 29 0.46040 42 43 -2166.0
6 3 -50.000 34 9 443.60 26 19 0.28270 21 29 59.020 43 43 0.0000
7 3 362.30 35 9 110.40 28 19 335.70 29 29 0.0000 1 44 220.30
8 3 25.340 36 9 114.55 29 19 161.00 35 29 85.700 2 44 86.460
9 3 140.10 37 9 -40.900 31 19 169.60 39 29 -71.000 3 44 30.040
10 3 23.390 39 9 97.040 33 19 136.90 44 29 -274.10 4 44 46.380
11 3 85.840 41 9 123.40 34 19 329.10 48 29 6.9710 5 44 -504.20
12 3 18.12 42 9 992.40 36 19 -42.310 1 30 354.55 7 44 -452.20
13 3 52.130 47 9 156.40 37 19 335.20 2 30 262.90 8 44 -659.00
14 3 -44.850 50 9 278.80 39 19 150.60 3 30 -64.690 23 44 -35.680
15 3 -22.310 1 10 677.00 41 19 -61.600 4 30 48.490 25 44 -209.7
16 3 -223.90 2 10 448.80 47 19 119.20 5 30 -120.50 29 44 1004.0
17 3 247.50 3 10 347.30 1 20 663.50 6 30 -61.76 31 44 -262.00
18 3 31.870 4 10 586.60 2 20 318.90 7 30 188.00 38 44 26.350
19 3 -22.970 5 10 -203.60 3 20 537.40 9 30 -163.70 44 44 0.0000
20 3 62.320 6 10 306.40 4 20 872.30 11 30 202.30 1 45 -5.8690
21 3 4.6800 7 10 -116.00 5 20 199.00 13 30 170.10 3 45 -88.110
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13 4 65.690 25 11 -171.1 17 21 287.00 23 32 86.400 49 49 0.0000
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1 5 986.50 37 12 134.50 21 22 108.30 2 34 31.140 24 56 127.16
2 5 524.10 39 12 -116.70 22 22 0.0000 3 34 154.26 25 56 8.48
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10 5 529.00 7 13 540.50 35 22 -215.00 19 34 -203.00 53 5 244.67
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12 5 139.40 9 13 -103.60 39 22 397.24 34 34 0.0000 53 7 833.21
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1 6 697.20 6 14 359.30 6 24 -44.760 36 36 0.0000 54 28 434.32
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22 6 669.90 5 15 42.700 28 24 -60.710 24 37 187.10 20 55 88.09
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39 38 50.06
40 38 185.6