ENVE 2001 – Final

Review
 Final Exam
3 problems (similar to the midterm and assignment questions)
Problem 1: Mass Balance
Problems 2 and 3: Energy Balance

• Know how to use compressibility charts and

psychrometric charts

• Understand the dew point and using Antoine Equation

• Understand phase changes (generally); what happens

when you reduce / increase pressure, temperature,
volume

• Understand excess air and combustion reactions

• Understand energy balances, what does each term

represent

• You can use either energy balance method to solve long

 Wet Specific
bulb line Enthalpy
(Adiabatic deviation
cooling) (KJ / kg BDA)

%RH = 100%
(saturated) Constant
Humidity Line
(or Dew Point
Line)

Specific
humid
volume line
(m3 / kg
Constant
Dry Temperature (C) BDA)
relative humidity (%RH)
Enthalpy on Psychrometric
Charts
Reference state is dry air and liquid water at 0C
Therefore, dry air at 0C has 0 KJ. Any water in the air
is relative to liquid water at 0C.

Uses wet bulb lines for “saturated enthalpy”

If not fully saturated there is less water in the air and

thus less total enthalpy – also use the “enthalpy
deviation lines”
 Enthalpy Specific
at Enthalpy
Saturation deviation
(adiabatic (KJ / kg BDA)
cooling)
Humidity & Relative
Humidity
Relative Humidity (RH) = pH2O / p*H2O

%RH = pH2O / p*H2O x 100%

Humidity (h) = mH2O(air) / mdry air

Tells you how much water is in the air

If no condensation or mixing occurs, humidity stays
constant
Vapor Pressure – p vs p*
Partial pressure (pi ) vs Vapor pressure (p*i)

Partial pressure (pi ) = pressure exerted by a gas i in a mixture

pi/PT = ni/nT  pi = PT x ni/nT

Vapor pressure (p*i) = pressure of gas (or vapor) i in equilibrium

with its liquid
- Depends only on Temperature for a given species

At Dew Point or Saturation, pi = p*

Antoine Equation
Empirical equation used to predict p* from T:

ln(p*) = A – [B / (C + T)]

where:
A,B,C = constants for each substance
p* = vapor pressure at T
T = temperature

Beware of the units for A, B, C. They can vary depending K or oC, and
for different Pressure units (kPa, atm, bar, mmHg)
(I will tell you which units apply)
 Real Gases (high P)
PV = znRT
From compressibility charts, z can be found based on Tr
and Pr
• Tr = critical temperature = T / Tc
• Pr = critical pressure = P / Pc
• vri = critical specific volume = v / vci
where vci = RTc / Pc

Note: don’t need to use vri often because is Tc, Pc are

known we can use Tr, Pr to find z
Real Gas Mixtures
Kay’s Method: use mole fractions to find P’c and T’c

P’c = PcA*xA + PcB*xB + …

T’c = TcA*xA + TcB*xB + …

Use P’c and T’c to estimate Pr and Tr for the mixture

using compressibility chart or Pitzer correlation
Chart 2
 Chart 3

Chart 2
Enthalpy (H)
• 
Enthalpy (H) is a measure of energy that includes internal energy
(U), but also accounts for pressure (p) and volume (V) of the
system.

For most practical purposes, the enthalpy change (at constant

pressure) can be expressed as:

Where Cp is the heat capacity at constant pressure.

 Heat of Formation

•is  the enthalpy change caused by formation of 1 mol of

a compound from its elements in the standard state at
25oC, 1 atm.

The o denotes “standard” (referring to the standard

state)

Therefore, for ALL elements in their normal reference

state:
(25oC, 1 atm), = 0
 Steady State, Open Systems
 

flows

Most often, the values of PE and KE are negligible in open systems:

Hflows

Hout - Hin
2 Methods to Solving Energy
Balances w Reaction

1: Heat of Formation & Sensible Heat Method

2: Heat of Reaction Method

Heat of Formation & Sensible Heat Method

•Just
  add up all H of the system and subtract (out – in):

Where each H term is relative to :

- Much simpler to use

- Good for determining overall heat released from system
- Not as good if we just want to know specifically how much produced by the
reaction
- Note: if is provided in a different phase, we need to account for latent heat
()
Heat of Reaction Method
•Solves
  for Hout - Hin indirectly by looking at how much heat
is produced (or consumed) in the reaction and how much
of this heat is absorbed or released by other components.

3 steps:

1. Find Standard Heat of Reaction (assumes 25oC):

-

- Don’t forget stoichiometric coefficients for each term

Heat of Reaction Method
•  Adjust heat of reaction for the actual temperatures
2.

Where is the sensible heat (and latent) relative to 25C:

- Again, don’t forget stoichiometric coefficients for each term

- Don’t need to include heat of formation – already included
in
Heat of Reaction Method
•   that the following:
Note

Is the same as:

• We are bringing all our reactants from T to 25C

• Then apply the standard heat of reaction at 25C
• Then bring the products from 25C to T
 Another way to look at it:

CO2@70C H2O@70C

∆  H ∆  H
 
= CH4 + 2O2  CO2 + 2H2O (at 25C)
∆  H ∆  H
CH4@20C O2@20C
Heat of Reaction Method
• 
Step 3. Account for any heat absorbed by non-reactants

+ non-reactants

+ ] non-reactants

• Don’t need to include heat of formation for things that

don’t react (same mol in vs same mol out, but at
different temperature and sometimes different phases)
Heat of Reaction Example

CH4 + 2O2  CO2 + 2H2O

1 mol CH4 1 mol CO2

10C 100C
2 mol O2
2 mol H2O
50C
100C
 Heat of Reaction Example

CH4 + 2O2  CO2 + 2H2O

 From tables (or given in problem statement):
= -74.8 KJ/mol
= -241.8 KJ/mol
= -393.5 KJ/mol
Cp, gases = 30 J/mol K

= -393.5 + 2(-241.8) – (-74.8) - 2(0)

= -802.3 KJ
Heat of Reaction Example
• 

+ (25C – 10C) (25C – 50C) + ( 100C – 25C)

No other species that go un-reacted so we can skip step 3.

Q = = - 796.6 KJ
Heat of Reaction Example
•   tells us how much heat is released by the reaction at the
Note:
given temperatures of reactants and products

Often we have other material coming in or out that may absorb

some of this heat.

Say we also had 10 mol N2 coming in at 50C and leaving at 100C:

Q = + 10 x Cp, N2 (100C - 50C)
= - 796.6KJ + 10mol x 30J/mol K x 50C / (1000J/KJ)
= - 796.6KJ + 15 KJ = - 781.6KJ

So after the N2 absorbs 15KJ, there is 781.6KJ or heat that can be

released from the system
Same Problem using Heat of Formation Method:

CH4 + 2O2  CO2 + 2H2O

Q

1 mol CH4 1 mol CO2

10C 100C
2 mol O2
2 mol H2O
50C
100C

10 mol N2 10 mol N2
50C 50C
Same Problem using Heat of Formation Method:

•   by finding all mol in and out:

Start

In: Out:
1 mol CH4 @ 10C 1 mol CO2 @ 100C
2 mol O2 @ 50C 2 mol H2O @ 100C
10 mol N2 @ 50C 10 mol N2 @ 100C

Then for each species, calculate :

 Same Problem using Heat of Formation Method:

• 
Enthalpy In:
1 mol CH4 @ 10C:
=
= 1 x (-74.8 KJ/mol + 30J/molK (10C-25C)(1KJ/1000J)
= -75.25KJ
2 mol O2 @ 50C
=
= 2 x (0 + 30J/molK (50C-25C)(1KJ/1000J)
= 1.5KJ
10 mol N2 @ 50C
=
= 10 x (0 + 30J/molK (50C-25C)(1KJ/1000J)
= 7.5KJ
 Same Problem using Heat of Formation Method:

• 
Enthalpy out:
1 mol CO2 @ 100C:
=
= 1 x (-393.5 KJ/mol + 30J/molK (100C-25C)(1KJ/1000J)
= -391.25KJ
2 mol H2O @ 100C
=
= 2 x (-241.8KJ/mol + 30J/molK (100C-25C)(1KJ/1000J)
= -479.1KJ
10 mol N2 @ 100C
=
= 10 x (0 + 30J/molK (100C-25C)(1KJ/1000J)
= 22.5KJ
 Same Problem using Heat of Formation Method:

•  = Hout - Hin
Q
Q = [(-391.25) + (-479.1) + (22.5)] - [(-75.25) + (1.5) + (7.5)]
Q = [-847.85] – [-66.25]
Q = - 781.6 KJ
Solving energy balance summary:

•  Approach 1: enthalpy of reaction

calculate energy released/consumed by the chemical
reaction(s)

• Approach 2: enthalpy of formation + sensible heat

calculate the amount of energy that materials carry in
and out

If the system consists of many chemical reactions, approach 2

is most likely faster than approach 1

If the reaction consists of many reactants and products,

approach 2 is most likely faster than approach 1

• Pay attention to unit (kJ/kg vs. kJ/mole, J/mol vs kJ/mol)

• Pay attention to phase transition (don’t forget )

1. Solving Mass / Energy Balance
Problems

- General Approach
 General Approach to
Solving Material Balance
Problems
1. Read and understand the problem statement
2. Sketch the process flow diagram (PFD)
3. Label all known values on the PFD streams (flows, composition,
materials)
4. Obtain any missing data (e.g. density, MW, constants, etc)
5. Select control volume and basis
6. Determine the # of unknown variables
7. Write out all known material balance equations and other
relationships from problem statement
8. Determine the # of independent equations (& degrees of freedom)
9. Solve the equations and answer the question
10. Check your work
We can often skip this step
Step 1: Read the problem carefully and try to
understand the process. Balance all reactions

Step 2: If not already given, sketch the diagram

describing the process.

Step 3: Populate the flow diagram with as much

information as possible. Identify the type and amount
of materials coming in and out at each ins and outs.

Step 4: Obtain any missing data (MW, density,

humidity, etc)

Step 5: Select a control volume and basis

Tutorial 10, Q2
Tutorial 10, Q2
Tutorial 10, Q2
Tutorial 10, Q2
Not needed if we use the right control volume!
Step 5: Select a control volume and basis.

Goal: to simplify the calculation

• Consider units: kg vs. mole, mass fraction vs. mole

fraction. Try to minimize the need to convert unit. (Unit
conversion is where students tend to make mistake
the most!)

• Mol are often easy to start with, but depends what

information is provided
• e.g. if composition of a fuel is given as %mass,
probably easier to start with a basis of say 100g of
fuel

• May need to make conversion at the end

e.g. problem asks you for kg CO2 produced from
500 kg CH4
Option 1: start with 500 kg CH4 and convert to
mol at the start
Option 2: assume a basis of, say 100 mol CH4,
then make an adjustment/conversion at the end

• Work with numbers that aren’t excessively large or

Energy Example 6 in class

100 g CaCO3

Basis: 100 g CaCO3 comes in

Energy Example 6 in class

Basis: 100 g CaCO3 comes in

6% CaCO3  m CaCO3 = 100x0.06

= 6g
Energy Example 6 in class

Basis: 100 g CaCO3 comes in

6% CaCO3  m CaCO3 = 100x0.06

= 6g
Wrong: mass that comes out is not
Energy Example 6 in class

Basis = 1 mol (or start with mass and convert to

mol)
CaCO3  CaO + CO2
Don’t know how much CaCO3 reacted, call it “x”

Solid stream out is 1 – x mol CaCO3 and x mol

CaO

6% = mCaCO3 / (mCaCO3 + mCaO)

Energy Balance Example 4
Energy Balance Example 4
What Basis to use?

In: 500kg/hr NH3, 8000kg/hr air

*The mixing ratio is important!

Option 1: Take the basis as given

500kg/hr NH3 (or call it 1 hr)

Then the mass flow rate of air is 8000kg/hr

Start this problem by converting everything to mol

500kg NH3 / 17g/mol = 29.4 kgmol NH3 or 29,400 mol NH3

8000kg air / 28.8g/mol x 0.21 = 58.3 kgmol O2

8000kg air / 28.8g/mol x 0.79 = 219.4 kgmol N2

Recall, average molecular weight of air = 0.79 x 28g/mol + 0.21 x 32g/mol = 28.8g/mol

Note: we could also use 500g NH3 and 8000g air, and multiply final answer by 1000
Energy Balance Example 4

What Basis to use?

Option 2: assume a new basis

Basis = 100 mol NH3 in

Mass air = 100 mol NH3 x 17g/mol x (8000g air / 500g NH3) = 27,200g air

27,200g air / 28.8g/mol x 0.21 = 198.3 mol O2

27,200g air / 28.8g/mol x 0.79 = 746.1 mol N2

Then solve for m H2O and make a conversion to final answer:

m H2O = 4.212kg H2O (per 100 mol NH3)

m H2O per 500 kg NH3 =

4.212kg H2O x 500kg NH3/100mol NH3 x 1000g/kg / 17g/mol = 1239kg

Step 6: Read the question again and identify
unknowns

Step 7: Set up mass and energy balance equations

Step 8: Calculate Degrees of Freedom (not necessary

for this class)

Step 9: Solve the equations and answer the question

Step 10: Review your work

At the end of the day, mass and energy in
the system have to be balanced.

If mass balance is incorrect, energy

balance will be incorrect (and vice versa)