Inchemistry, theECW model is a semi-quantitative model that describes and predicts the strength ofLewis acid–Lewis base interactions. Manychemical reactions can be described asacid–base reactions, so models for such interactions are of potentially broad interest. The model initially assignedE and C parameters to each and every acid and base. The model was later expanded tothe ECW model to cover reactions that have a constant energy term,W, which describes processes that precede the acid–base reaction. This quantitative model is often discussed with the qualitativeHSAB theory, which also seeks to rationalize the behavior of diverse acids and bases.

As early as 1938,G. N. Lewis pointed out that the relative strength of an acid or base depended upon the base or acid against which it was measured.^[1] No single rank order of acid or base strength can predict the energetics of the cross reaction. Consider the following pair of acid–base reactions:.

4F-C₆H₄OH + OEt₂ −ΔH = 5.94 kcal/mole

4F-C₆H₄OH + SMe₂ −ΔH = 4.73 kcal/mole

These data suggest that OEt₂ is a stronger base than SMe₂. The opposite is found, however, when I₂ is the acid:

I₂ + OEt₂ −ΔH = 4.16 kcal/mole

I₂ + SMe₂ −ΔH = 7.63 kcal/mole

TheE-C model accommodates the failure of single parameter descriptions of acids and bases. In 1965Russell S. Drago and Bradford Wayland published the two term equation such that each acid and each base is described by two parameters.^[2] Each acid is characterized by anE_A and aC_A. Each base is likewise characterized by its ownE_B andC_B. TheE andC parameters refer, respectively, to theelectrostatic andcovalent contributions to thestrength of the bonds that the acid and base will form. These parameters have been empirically obtained by using enthalpies for adducts that form onlyσ bonds between the acid and base as well asadducts that have nosteric repulsion between the acid and base.

${\displaystyle -\mathrm{\Delta }H=E_A{E}_B+C_A{C}_B}$

This equation reproduces and predicts theenthalpy, ΔH, of a reaction between many acids and bases. ΔH is a measure of strength of the bond between the acid and the base, both in the gas phase and in weakly solvating media.Entropy effects are ignored. A matrix presentation of the equation enhances its utility.^[3]

Four values, twoE and twoC were assigned as references.E_A andC_A ofI₂ were chosen as standards. Since I₂ has little tendency to undergo electrostatic bonding, theE_A parameter was assigned a small value, 0.5, while the value ofC_A for the covalent property was set at 2.0. For the two base parameters,E_B for CH₃C(O)N(CH₃)₂ (DMA) was set at 2.35 andC_B for (C₂H₅)₂S,diethyl sulfide, was set at 3.92. Fixing the parameters in this way imposed the covalent-electrostatic model on the data set by fixing theE_AE_B andC_AC_B products of the DMA and (C₂H₅)₂S adducts with iodine, and these four values ensured that none of the parameters had negative values. Due to increasing enthalpy data that became available since the EC equation was first proposed the parameters have been improved. MixingE andC numbers from the improved set of parameters with older parameters will result in incorrect calculations and is to be avoided.^[4] A select set of the improvedE andC numbers is found in this article and the complete set is available in the literature.^[5][6]E_B andC_B parameters for phosphines that can be used in combination with the improved parameters for oxygen, nitrogen, and sulfur donors to measure σ-basicity have been reported.^[7]

In theECW model, a new term W was added to the equation.

${\displaystyle -\mathrm{\Delta }H=E_A{E}_B+C_A{C}_B+W}$

The W term represents a constant energy for cleavage of a dimeric acid or base. For example, the enthalpy of cleavage the[Rh(CO)₂Cl]₂ by base B involves two steps. The first step is cleavage of the dimer, which isW:

⁠1/2⁠ [Rh(CO)₂Cl]₂ → Rh(CO)₂Cl W = −10.39 kcal/mol

The second step is the binding of B to RhCl(CO)₂monomer. In this case,W = −10.39 kcal/mol.

In other cases, W is the enthalpy needed to cleave the internal hydrogen bonding of the H-bonding acid(CF₃)₃COH. W is also useful for a base displacement reaction in poorly solvating media:

F₃B-OEt₂ → BF₃ + OEt₂

For any base, a constant energy contribution is observed for the breaking of theF₃B-OEt₂ bond. An ECW study of the enthalpies of a series of bases produces a W value that corresponds to the enthalpy of dissociation of the F₃B-OEt₂ bond. TheE_A andC_A parameters that result are those for uncomplexed BF₃.

A graphical presentation of this model clearly shows that there is no single rank order of acid or base strength, a point often overlooked, and emphasizes that the magnitude of acid and base interactions requires two parameters (E &C) to account for the interactions.^[8]

The EC equation from the ECW Model

${\displaystyle -\mathrm{\Delta }H=E_A{E}_B+C_A{C}_B}$

can be rearranged into a form which can be plotted as a straight line.

In a Cramer–Bopp plot for Lewis bases, the parameterR_a^[a] reflects the mode of bonding of a potential Lewis acid partner, from purely electrostatic interactions (R_a = −1) to purely covalent interactions (R_a = +1). The parameter${\displaystyle \frac{-\mathrm{\Delta }H}{E_a+C_a}}$ reflects the strength of the bonding interaction. The plot shown here allows comparison of three chosen Lewis bases:acetonitrile,ammonia, anddimethyl sulfide. The Lewis acid iodine (R_a = 0.6) will interact most strongly with dimethyl sulfide and least strongly with acetonitrile, whereastriethylgallium (R_a = −0.65) will interact most strongly with ammonia and least strongly with dimethyl sulfide. The plot also shows that ammonia is a stronger Lewis base than acetonitrile irrespective of its Lewis acid partner, whereas the relative strengths of ammonia and dimethyl sulfide as Lewis bases depends on the bonding characteristics of the Lewis acid, swapping order whenR_a = 0.1.(NB: guesstimate).^{[clarification needed]} The Cramer–Bopp plot was developed as a visual tool for comparing Lewis base strength with the range of possible Lewis acid partners, and a similar plot can be constructed to examine selected Lewis acids against the range of possible Lewis bases. References 5, 8, 12, and 14 contain graphical presentations that define the ranking order of strength of many Lewis acids and bases.

As mentioned above theE andC parameters are obtained from enthalpies of adduct formation in which the bond between the acid and base is a σ interaction and adducts that have no steric repulsion between the acid and base.As a result,E andC parameters can be used to glean information aboutpi bonding. When pi bonding contributes to the measured enthalpy, the enthalpy calculated from theE andC parameters will be less than the measured enthalpy and the difference provides a measure of the extent of the pi bonding contribution.^[9][10]

The ᐃH calculated for the reaction ofMe₃B with Me₃N is larger than the observed. This discrepancy is attributed to steric repulsion between the methyl groups on the B and N. The difference between the calculated and observed values can then be taken as the amount of thesteric effect, a value otherwise not attainable. Steric effects have also been identified with(CH₃)₃SnCl and withCu(HFacac)₂.

The use ofE andC parameters have been extended to analyze spectroscopic changes occurring during adduct formation.^[11] For example, the shift of the phenol OH stretching frequency,Δχ, that occurs upon adduct formation has been analyzed using the following equation:

Δχ =Ε_A^∗E_B +C_A^∗C_B +W^∗

where asterisks on theE_A andC_A for phenol indicate that the acceptor is held constant and the frequency shift is measured as the base is varied. The asterisks also indicate that the phenol parameters are those for frequency shifts and not those for enthalpies. An analysis like this provides a basis for usingE_B andC_B parameters as a reference scale of donor strengths for frequency shifts. This type analysis has also been applied to other spectroscopic shifts (NMR,EPR,UV-vis,IR, etc.) accompanying adduct formation. Any physicochemical property,Δχ, that is dominated by σ donor-acceptor interaction can be correlated with the enthalpy-derivedE andC parameters.

TheECW equations enables one to correlate and predict the enthalpies of adduct formation of neutral donor-acceptor interactions for which the electron-transfer is limited. For gas-phase reactions between cations and neutral donors, there is significant electron-transfer. The extension of theECW model to cation-neutral Lewis base interactions has led to theECT model.^[12][13] Others have concluded that the ECW model "is generally found helpful in many fields of solution chemistry and biochemistry".^[14]

The enthalpies of formation of some Donor-I₂ adducts are listed below. I₂ is a Lewis acid classified as asoft acid and its acceptor properties are discussed in the ECW model. The relative acceptor strength of I₂ toward a series of bases, versus other Lewis acids, can be illustrated by C-B plots.^[15]

• Acid–base reaction
• Lewis acid–Lewis base
• Acid
• Russell S. Drago

• Acid–base chemistry
• Inorganic chemistry

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