Adamson, Cap.

III-1c
Effect of Curvature on Vapor Pressure

Effect of a change in mechanical pressure P at constant T on molar free energy G

𝑑𝐺 = −𝑆𝑑𝑇 + 𝑉𝑑𝑃

at T constant 𝑑𝐺 = 𝑉𝑑𝑃 !"

𝚫Pyoung-laplace = cos𝜃
ΔG = ∫ VdP
#

If molar volume V constant Correlation with curvature:Young-Laplace

2𝛾 2𝛾𝑉
∆𝐺 = 𝑉∆𝑃 ∆𝑃 = ∆𝐺 =
𝑟 𝑟
Correlation with vapor pressure
1 𝑃!"#$% 2𝛾𝑉
𝑃𝑉 = 𝑅𝑇 𝐺 = 𝑅𝑇 , 𝑑𝑃!"#$% ∆𝐺 = 𝑅𝑇𝑙𝑛 =
𝑃!"#$% !
𝑃!"#$% 𝑟
 Adamson, Cap. III-1c
Effect of Curvature on Vapor Pressure

Kelvin Equation

𝑃!"#$% 2𝛾𝑉
For spherical surface 𝑅𝑇𝑙𝑛 ! =
𝑃!"#$% 𝑟

𝑃!"#$% 1 1
For elliptical surface 𝑅𝑇𝑙𝑛 = 𝛾𝑉 + R1 and R2 ortogonal to each other
!
𝑃!"#$% 𝑅( 𝑅)

!
𝑃!"#$% = normal vapor pressure of the liquid over flat surface
𝑃!"#$% = vapor pressure of the liquid over curvature
 𝑃!"#$% 2𝛾𝑉
𝑅𝑇𝑙𝑛 ! =
Kelvin equation 𝑃!"#$% 𝑟
P0 = normal vapor pressure of the liquid over a flat surface
P = vapor pressure of a liquid with over a curvature
Water
r = 10-4 cm (1 𝜇m) P/P0 = 1.001
r = 10-5 cm (100 nm) P/P0 = 1.011
r = 10-6 cm (10 nm) P/P0 = 1.114

Vapor pressure increases with curvature (smaller r)

Ability of vapors to supersaturate:

Formation of a new liquid phase: small clusters growing to droplets
Activation energy needed to increase the free energy due to curvature
(dust, foreign surfaces needed)
Nature 588 (2020) 250

Capillaries filled with water at certain relative humidity:

−2𝛾
𝑅𝐻$ = exp
𝑘% 𝑇𝑑𝜌&

Surface tension
𝛾 = 73 𝑚𝐽𝑚 '!
Number density of water molecules
𝜌& = 3.3 1028 m-3

kB=Boltzmann constant
!(
Capillary condensation (for contact angle near 0) in the range of d≈ ) ≈ 1.1nm
! *+"
or cylindrical pores smaller than 3nm. If less hydrophilic, even stronger confinement
 Kelvin equation

𝑃!"#$% 2𝛾𝑉 P0 = normal vapor pressure of the liquid over a flat surface
𝑅𝑇𝑙𝑛 ! = P = vapor pressure of a liquid with over a curvature
𝑃!"#$% 𝑟
!"
𝚫Pyoung-laplace = cos𝜃
#

r Vapor pressure of liquid in a

r
drop higher than for a flat
surface, but lower in a bubble

Large drops grow at the expense of small drops (evaporation from small drops and
condensation on larger drops)
Boiling water

𝑃!"#$% 2𝛾𝑉
𝑅𝑇𝑙𝑛 ! =
𝑃!"#$% 𝑟
https://www.youtube.com/watch?v=LpDs7Xm1uLo
 Oil gas recovery in Shale Reservoirs
Shale reservoir worldwide: 345 billions barrels of oil and 7299 trillion
cubic feet of gas
Kelvin equation

𝑃!"#$% 2𝛾𝑉 Extremely small pore size (<50 nm), low porosity, ultra-low permeability
𝑅𝑇𝑙𝑛 ! =
𝑃!"#$% 𝑟 Technology: horizontal drilling and multistage fracturing

Shale gas condensate reservoir

Problem: Condensate accumulates near the wellbore
(condensate blocking) reducing the gas production
Solution: gas injection
Energies 2019, 12, 2355; doi:10.3390/en12122355
 Kelvin equation Goodwin p. 211
Vapor pressure above liquid in capillary or pore is lower than above a flat surface
(although the total capillary pressure is higher)
Capillary condensation:
vapor condenses in fine pores or
cavities, prior to the saturation vapor
pressure is reached
Carbon Molecular Sieve and high free volume
Small r membranes for gas separation
low vapor pressure
r1

𝑃!"#$% 2𝛾𝑉
𝑅𝑇𝑙𝑛 ! =
Force holding
𝑃!"#$% 𝑟'
F
particles
together
Ostwald Ripening 𝑃!"#$% 2𝛾𝑉
𝑅𝑇𝑙𝑛 ! =
𝑃!"#$% 𝑟'

Large drops grow at the expense of small drops

http://www.crm.cat/en/Activities/Curs_2015-
(evaporation from small drops and condensation on 2016/Documents/AppliedNanoparticlesProb1.pdf
larger drops)
 Clouds and rain
Kelvin equation

𝑃!"#$% 2𝛾𝑉 Clouds: water condensation into droplets

𝑅𝑇𝑙𝑛 ! = Rain: heavy droplets
𝑃!"#$% 𝑟 Snow: air < 0oC

Homogenous nucleation
2𝑀𝛾
𝑟@ =
𝑃!"#$%
𝜌𝑅𝑇𝑙𝑛 !"#$%!
𝑃
𝜌 = density of the liquid
M = molecular weight of the liquid
Liquid from vapor
6-8 fold supersaturation
Ice from liquid at -40oC

Henry Houghton Cloud Physics Science 1959

Cloud seeding Magritte

Static cloud seeding spreading silver iodide into clouds.
Hygroscopic cloud seeding disperses in the clouds. The salts
grow in size as water joins with them
 Water vapor harvesting nanostructures

Linda Zou, UAE

Science 2020, 368, 1303
 Maximum Bubble Pressure Method

ΔP is maximum, r = tube radius

(external for non-wetting liquids
Internal for wetting liquids)

2γ
t ΔP =
r

Experimental: Maximum ΔP such that bubbles are unable to grow and break away
(maximum ΔP = Pmax – Pt)

Tube must be small, corrections for r/a > 0.05 needed

Detachment Methods

Drop weight method

Ring Method

Wilhelmy Slide Method

 Drop weight method

Tate’s law (1864)

Drop weight W = 2π rγ f
Maximum force to support the drop weight is the surface tension force per cm x tip circunference
(correction factor f is needed in most cases; for non-wetting liquid, r is the internal radius)
Dynamic method useful for adsorption studies