ENGN

0720
Thermodynamics

Lecture Slides
Thursday, February 6th

Robert Hurt, today’s instructor

Today’s topic:
1st law for open systems

Spring Semester 2020

Recap Example application: Technological use of varying hydrocarbon (CHO) fuels
Uses determined by PVT and phase behavior !

Fuel Tn Tcr Preferred

(normal (critical Phase at storage / use
Formula Name boiling pt) temperature) room T,P methods
CH4 Methane (nat gas) -161 C -82 C gas Cryogenic, high-P
pipeline gas
C3H8 Propane -42 C 97 C vapor As liq (Psat ~ 6 bar)
grills, campers
C4H10 Butane ~ 0 C 152 C vapor As liq, P> 1 bar
hand-held lighters
C8H18 Octane (gasoline) 126 C 296 C liq Liq, atm P; spark engines

C10H22 Decane (Diesel fuel) 174 C 345 C liq Liq, atm P; Diesel engines

H2 Hydrogen -253 C -240 C gas Not yet widely used

(20.4 K) (33.2 K)
(~ C5H5O) Coal --- solid
---

Biomass (wood) --- solid

(~ C4H3O3) ---
Recap

Thermodynamic Properties of Mixtures - A brief introduction

We have considered problems with multiple phases (gas/liq/solid), but always a single chemical substance

However, most samples or streams of interest to engineers contain multiple chemical substances
(e.g. O2, N2, H2O, CH4, H2 …)

Special note: “air” is a mixture (~79 mol-% N2, 21 mol-% O2 and other trace species
like Ar, CO2…), but is so common it is often treated as a pseudo-single-component substance)

Some Basic Mixture Definitions

Mole fraction ≡ Ni / Ntot; ∑ Xi = 1

Partial pressures, Pi (for gas or vapor mixtures): the pressure that a single component would exert on
the walls of its container (at same T,V) if present alone

General case: The state of an n-component mixture will be defined if we know n-1 mole fractions
plus two other variables. Having defined the state, any property “M” of that mixture will be defined
Recap

The Ideal Mixture (the model we use in ENGN0720)

U = ∑ Xi Ui
H = ∑ Xi Hi Where pure component values (Ui, Hi, Cpi Cvi)
Cp = ∑ Xi Cpi are evaluated at the same P and T
Cv = ∑ Xi Cvi
V = ∑ Xi Vi Note for ideal gas mixtures: P = ∑ Pi (sum of the partial pressures, Pi, where Pi = XiP)
∑Pi = ∑XiP P = P

This model is very powerful and often correct for gas mixtures (mixtures of ideal gases).
It is not so often applicable to liquid mixtures – most are non-ideal

At the molecular level, the ideal solution model is based on the idea that
intermolecular interactions between molecules A and B (red and blue below)
are similar to those between A and A and B and B.

A-B liquid A-B vapor

mixture mixture
Recap

Vapor Pressure
The Psat value for a liquid { Psat = f(T only) } is referred to as its “vapor pressure”
The vapor pressure can be thought of as a liquid property – the pressure the molecules
exert as they randomly leave the liquid phase

Simulation from
Univ. of Oregon
 Case 1: atmosphere atmosphere
Single
Component

(imagine H2O 1 2
at room T)
Heat à vapor

liquid
liquid

State 1 State 2

Case 2: Case 3: open system

atmosphere
Add a second component (a gas)
(imagine air) atmosphere (dry) (slightly humid)

atmosphere atmosphere Heat not

required
(but speeds
up
equilibration)
air liquid
air (+ water vapor)
(+ water vapor) Heat à
Start End
Liquid H2O
Liquid H2O

State 1 (for liquid) State 2 (for liquid)

Calculations combining the ideal gas Key ideas
mixture model with the vapor pressure
Vapor pressure is a liquid property!
(expresses liquid’s “desire” to create a vapor above itself)

atmosphere Pvap = “Psat” = f(T only)

(can be looked up on the sat liq line)

The relevant vapor property

is the partial pressure, Pi

Pi = Xi Ptot
air
(from ideal gas mixture model)
(+ water vapor)

Liquid H2O Liquid “tries” to create vapor by releasing molecules.

Equilibrium is reached when
Pi reaches Pvap

Xi Ptot = Psat(T)

Solve: Xi = Psat(T) / Ptot

 ENGN 0720
Today: 1st law, open systems ! Thermodynamics

Because open systems typically describe dynamic (time-

dependent) processes, let’s start with a formulation of
the energy balance that based on rates (derivatives)
Open
(mass crosses one or
more of its boundaries)

Differential
volume System at time t System at time t + dt

dE = dQ – dW + (Udm)in – (Udm)out + (PdV)in – (PdV)out Rate at which new

volume enters system

dE/dt = Q – W + [ m(U) ]in - [ m(U) ]out + (mPv)in - (mPv)out

Rate of change Heat Power Rate at which Rate at which volume/mass

of energy flow in out the entering mass exiting mass mass flow
within system brings in energy takes away energy

“flow work”
Since U + PV = H….........

dE/dt = Q – W + [ m(H) ]in - [ m(H) ]out

Rate of change Heat Power Rate at which Rate at which

of energy flow in out the entering mass exiting mass
within system brings in energy takes away energy

A good general form to remember for the 1st law for open systems

Notes:

dE/dt is often (in this course) reduced to dU/dt

This form is easily generalized to multiple mass inputs, S[ m(H) ]in , multiple outputs
or multiple heat flows or work flows

Important: Some (but not all) problems deal with open systems in “steady state” – these systems
operate in a way that processes some fluid and effects some change on the environment,
but the system Itself is not changing over time, and dE / dt = 0. All other system properties
must also remain the same (all time derivates are zero).
Example 1: Continuous dental air compressors

Find steady-state power requirement, kW

To air cooler

- Inlet: 27 C, 600 g/min air flow

- Outlet: 5 bar, 257 C
- negligible heat loss

0 0
dE/dt = Q – W + [ m(H) ]in - [ m(H) ]out

steady state

dM/dt = [m]in - [m]out

steady state W = m [ Hin – Hout ]

[m]in = [m]out W = - 2.3 kW

 Example 2: continuous (liquid) pumping
Find steady-state power requirement, kW

water, liq.

- Inlet: 27 C, 6 kg/min, 1 bar

- Outlet: 20 bar, 27 C
- negligible heat loss

0
This tire “pump”
dE/dt = Q – W + [ m(H) ]in - [ m(H) ]out is really a compressor : )

steady state

dM/dt = [m]in - [m]out W = m [ Hin – Hout ]

steady state

Need liquid water enthalpies

 W = m [ Hin – Hout ] Need liquid water enthalpies

We know DU = CvDT (incompressible substance) and Cv = Cp = C, so any “C” will do

Often we also use: DH = CpDT (incompressible substance) and Cv = Cp = C

But here DT = 0 and only the pressure is changing. This would give W = 0!

This is a special case. Go back to enthalpy definition

[ Hin – Hout ] = (U + PV)in – (U + PV)out

= (Uin – Uout) + [(PV)in – PV)out]

= 0 + V(Pin – Pout)

(.001 m3/kg) ((1-20)bar) (105 Pa/bar) (50kg/min)

[ Hin – Hout ] = = - 1.5 kW
(60 s/min) 1 (Pa-m3 / J)
The incompressible substance model
also gives us another simple way The incompressible substance tool kit
to get U or H for liquids or solids
V = f(T only) - and a weak function, often ignored
Cp = Cv = ”C”
U, ”C”= f(T only)
For U: !U = C!T; !H = !U + !(PV) = C!T + V!P

U = f (T only)
So, go to sat liq/vap tables and pull out Usat at correct T (even though P is incorrect!)

Example: what is U for liquid water at room T (20 C) and P (1 bar)?

(use table on next slide)

For H:
H = U + PV

DH = DU + PDV

if temperature is changing for a liquid/solid, then DH is normally dominated

by the T effect (and any P change is not so important)

Therefore H ≈ f(T only) and H can be pulled off table as Hsat liq at correct T
 1st law example – condensation by mixing

Cool liquid propane

20 bar, 20 C
What is the minimum liquid propane mass flow rate
needed to fully condense this vapor so it can be pumped?
Superheated
propane vapor
20 bar, 110 C
3 kg/s
to pump to storage

0 0 0
dE/dt = Q – W + S[ m(H) ]in - [ m(H) ]out

steady state
[m(H)vap]in + [m(H)liq]in = [m(H)]out Eq. 1
0
dM/dt = [mvap]in + [mliq]in - [m]out
steady state
[mvap]in + [mliq]in = [m]out Eq. 2
 1st law example – condensation by mixing

Cool liquid propane

20 bar, 20 C
What is the minimum liquid propane mass flow rate
needed to fully condense this vapor so it can be pumped?
Superheated
propane vapor
20 bar, 110 C
3 kg/s
to pump to storage

[m(H)vap]in + [m(H)liq]in = [m(H)]out Eq. 1

Two equations

[mvap]in + [mliq]in = [m]out Eq. 2

[mliq]in , [m]out , Hout Three unknowns

How to find Hout? P = 20 bar; phase = ? Sat liquid! Ans: mliq = 10.7 kg/s
 Today’s Second Topic:

Introduction to flow devices

the components used to build thermodynamic

devices and large-scale processes
 ENGN 0720
Thermodynamics

Assignment

Optional recommended reading, Chap. 4 (open systems)

Moran and Shapiro

Homework Set #1 due today

(now, or by 4 pm, 2nd floor)

Homework Set #2 will be posted tonight

(due next Thursday, 4 pm)