版权所有：华东理工大学物理化学教研室 6 The First Law: dU =dq+dw H pV U pV A TS G TS For a reversible change in a closed system of constant composition, and in the absence o f a n y n o n - e x p a n s i o n work: d w = -pdV and dq =TdS dU=TdS-pdV dU is an exact differential, its value is independent of path. The fundamental equations
版权所有：华东理工大学物理化学教研室 6 The First Law: dU =dq+dw H pV U pV A TS G TS For a reversible change in a closed system of constant composition, and in the absence o f a n y n o n - e x p a n s i o n work: d w = -pdV and dq =TdS dU=TdS-pdV dU is an exact differential, its value is independent of path. The fundamental equations
版权所有：华东理工大学物理化学教研室 7 H pV U pV A TS G TS dH = dU+ pdV + Vdp =(TdS-pdV)+ pdV + V dp H=U+pV, A=U-TS, G=U+pV-TS dA= dU-TdS-SdT = (TdS -pdV) -TdS- SdT dG = dU+pdV+ Vdp –TdS- SdT = (TdS-pdV) +pdV+ Vdp –TdS- SdT = TdS +V dp = Vdp -SdT = -p dV -SdT The fundamental equations
版权所有：华东理工大学物理化学教研室 7 H pV U pV A TS G TS dH = dU+ pdV + Vdp =(TdS-pdV)+ pdV + V dp H=U+pV, A=U-TS, G=U+pV-TS dA= dU-TdS-SdT = (TdS -pdV) -TdS- SdT dG = dU+pdV+ Vdp –TdS- SdT = (TdS-pdV) +pdV+ Vdp –TdS- SdT = TdS +V dp = Vdp -SdT = -p dV -SdT The fundamental equations
版权所有：华东理工大学物理化学教研室 8 dU=TdS -pdV dH=TdS+Vdp dG=Vdp-SdT dA=-pdV-SdT H pV U pV A TS G TS The fundamental equations The fundamental equations
版权所有：华东理工大学物理化学教研室 8 dU=TdS -pdV dH=TdS+Vdp dG=Vdp-SdT dA=-pdV-SdT H pV U pV A TS G TS The fundamental equations The fundamental equations
版权所有：华东理工大学物理化学教研室 9 5.1 Properties of the internal energy 1). The Maxwell relations = gdx + hdy z = f ( x , y) y y z x x z z y x d d d ⎟⎟⎠⎞ ⎜⎜⎝⎛ ∂∂ ⎟ + ⎠⎞ ⎜⎝⎛ ∂∂ = y x y z h x z g ⎟⎟⎠⎞ ⎜⎜⎝⎛ ∂∂ ⎟ = ⎠⎞ ⎜⎝⎛ ∂∂ where =
版权所有：华东理工大学物理化学教研室 9 5.1 Properties of the internal energy 1). The Maxwell relations = gdx + hdy z = f ( x , y) y y z x x z z y x d d d ⎟⎟⎠⎞ ⎜⎜⎝⎛ ∂∂ ⎟ + ⎠⎞ ⎜⎝⎛ ∂∂ = y x y z h x z g ⎟⎟⎠⎞ ⎜⎜⎝⎛ ∂∂ ⎟ = ⎠⎞ ⎜⎝⎛ ∂∂ where =
版权所有：华东理工大学物理化学教研室 10 1). The Maxwell relations x y z y g x ∂ ∂ ∂ = ⎟⎟⎠⎞ ⎜⎜⎝⎛ ∂∂ 2 y x z x h y ∂ ∂ ∂ ⎟ = ⎠⎞ ⎜⎝⎛ ∂∂ 2 x y x h y g ⎟⎠⎞ ⎜⎝⎛ ∂∂ = ⎟⎟⎠⎞ ⎜⎜⎝⎛ ∂∂ dz = gdx + hdy The first derivative of g with respect to y, and h to x 5.1 Properties of the internal energy
版权所有：华东理工大学物理化学教研室 10 1). The Maxwell relations x y z y g x ∂ ∂ ∂ = ⎟⎟⎠⎞ ⎜⎜⎝⎛ ∂∂ 2 y x z x h y ∂ ∂ ∂ ⎟ = ⎠⎞ ⎜⎝⎛ ∂∂ 2 x y x h y g ⎟⎠⎞ ⎜⎝⎛ ∂∂ = ⎟⎟⎠⎞ ⎜⎜⎝⎛ ∂∂ dz = gdx + hdy The first derivative of g with respect to y, and h to x 5.1 Properties of the internal energy