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what are the 8 substances that make up the chemical composition of water?
H20, pH, major cations, major anions, organic matter, trace metals, particles, biological materials.
Give 4 examples of chemical reactions
sorption-desorption, acid-base, precipitation-dissolution, redox
Give 2 examples of biological processes
uptake and release, photosynthesis and respiration
What is the equation for advection
concentration x mean velocity
What are 2 types of diffusion
Eddy turbulence and molecular
What is the equation for diffusion
concentration gradient x diffusion coefficient
3 key facts regarding thermal stratification
Bottom waters horizontally mixed, surface waters mixed by convection, eddy diffusion controls vertical transport
Define eddy diffusion
The diffusion process where substances are mixed due to eddy motion
Example of eddy diffusion
Manganese- released from sediment and diffuses through the stratified bottom layers, well mixed in surface waters.
What is the exponential decay curve equation
C = Coe^-Q/v
What does the exponential decay curve equation show?
How the concentration of a substance decreases with time
What are steady-state conditions, an example and exception
Where the total mass in the compartment equals the rate of input or output. Chemical equilibrium, except slow processes such as weathering
What are non steady-state conditions, an example and exception
Where there is a change in concentration over time, for example in lakes. Chemical disequilibrium, except very fast reacting element under input-output balance
Define residence time
The mean time period that any constituent remain in a specified compartment.
What is the average residence time in the oceans compared to windermere
4000 years to 1 year
What are 3 factors that affect the distribution of substances
Reaction rate, residence time, internal mixing
What does an increase in the residence time suggest
A more complex reaction that is heterogeneous and involves physical mixing
What is the shape of a water molecule
4 tetrahedrally orientated sp3 orbitals
How is polarity produced in the water molecule (2 factors)
A difference in electronegativity between O and H, and the distribution of lone electron pairs
What is a hydrogen bond
electrostatic attraction between H and O
in separate H2O molecules, which links 4-8 molecules so it has a higher effective molecular weight
What substances are soluble
Ionic and polar covalent substances
What substances are insoluble
covalent substances (e.g. PCB)
What 2 factors is solubility linked to
Hydration and the dielectric effect of water (as water has no charge, it electrostatically insulates charged ions in a solution).
What is the size of truly dissolved substances and example
less than 1 nm, viruses
What is the size of colloids and example
1 nm - 1 macrometer, bacteria and algae
What is the size of particulates
More than 1 micrometer
2 factors about transport and location of colloids
Suspension of small particles, dispersed in water with dissolved substances
Define stokes law
where the velocity of gravitational settling is proportional to diameter squared
For particles less than 1 micrometer, why can they not compete with other forces (examples)
because their velocity is too small to compete with Brownian motion and turbulence
4 key properties of colloids
very large specific surface area, reactive, mobile and act as intermediates in solution (particle coagulation)
3 examples of colloids
Sulphide minerals, organic materials, clay minerals
Define chemical speciation
substances with different chemical and physical forms with different chemical and biological properties
When is the Physical form important in speciation
Metal ion in solution vs metal adsorbed to clay particles
When is the Physical form unimportant in speciation and example
Free hydrated metal ions vs metal complexes with inorganic ligands, free hydrated Fe2+ behaves differently to Fe(II)-humic complex (forms insoluble FeS)
What happens with chemical speciation in algae
Only free ions are taken up by the algae (Free Ion Activity Model)
Two examples of chemical speciation and biological uptake
Zn Uptake by Algae, zinc concentration in the water was linear to zn2+ in the blue-green algae. Al Uptake by Fish, Al is bad for fish, in high pH and more humic-rich waters, less Al3+ available so fish are safe
What is chemical speciation important for (biological)?
important for bioavailability of substances
What are the key biological substances that affect the chemical composition of natural waters
micro-organisms such as planktonic algae and bacteria
2 major factors that affect chemical speciation, and example
pH and dissolved organic compounds, Metal ion plus humic acid = metal humic species
What size is the filter for filtration
0.1-1 micrometer
2 problems with filtration
Dissolved substances generally includes the colloidal fraction, and size fractions are also affected by other properties
What 4 factors affect the size fractions in filtration
non-uniform pore sizes, clogging, adsorption onto filter and apparatus, colloidal aggregation
Describe the example of measuring total dissolved substances by colorimetry
Phosphate analysis, acidified molybdate reagent. Produces reduced phospho-molybdate complex that absorbs long wave-length visible light. Intensity of blue colour is proportional to concentration. Includes free orthophosphate and inorganically complexed orthophosphate.
Describe the example of measuring total dissolved substances by atomic absorption spectrometry
Sample is sprayed into the flame and atomised. Light with suitable wavelength is shone through the flame. Light is absorbed by the atoms of the sample. The amount of light absorbed is proportional to the concentration of the element in the sample.
How are free ions analysed?
By Ion Selective Electrode (ISE). A membrane electrode possesses a certain selectivity towards a given ion or ions
Define free hydrated metal ions
No ligands other than the water molecules
Define complexes
Central ion or atom surrounded by ligands
Define ligands
Molecules or ions in metal complexes
How do you measure free ions?
Using a ion selective electrode (ISE)
Define an ion selective electrode
A membrane electrode that possesses a certain selectivity towards a given ion or ions
How do you measure labile species
Anodic stripping voltametry (ASV) or diffusive gradient in thin films (DGT)
Define labile species
Species that can dissociate in response to pertubation
4 advantages of DGT
In situ, time-integrated, measures labile and bio-available species, not affected by environmental conditions
What is the equation used by DGT
C = m delta g / DAt
3 reasons why the concentration of labile species measured using DGT be smaller than using a filter?
Diffusion coefficient could be smaller, complexes may dissociate slowly, DGT doesn't measure colloids
what 5 things does DGT measure?
metals, radionuclides, nutrients, antibiotics, pesticides
What is the main dissolved constituent in natural waters?
inorganic ions
What 3 things does the concentration of inorganic ions depend on?
crustal abundances, aqueous chemistry, biological effects
Give 3 examples of very soluble metal ions
Calcium, sodium, magnesium
Give 2 examples of not very soluble metal ions
Aluminium and iron
Define ionic potential
a charge density term indicating the ionizing power of the ion
What is the equation for ionic potential
ionic potential (z/r) = Ionic charge (z) / ionic radius (r)
What does the interaction strength of elements in dissolved water depend on?
ionic potential
What happens to ions when there is a low ionic potential (under 3) and a low cation electronegativity (under 1.2)
Large, low-charge, electropositive ions surrounded by water molecules with little interaction between ion and water
What happens to ions when there is a medium ionic potential (3-12) and a medium cation electronegativity (1.2-1.9)
Small, highly-charged, electropositive ions, interaction between ion and water, bond to oxygen by abstracting OH liberating hydrogen ion, form uncharged and insoluble hydroxides (Fe, Al)
What happens to ions when there is a high ionic potential (over 12) and a high cation electronegativity (over 1.9)
Smaller, more highly-charged, electronegative ions, interaction between ion and water, bond to oxygen by abstracting O liberating hydrogen ion, form large and stable anions
The elements present in highest concentrations relative to their crustal abundances are...
group 1 metals and the larger group 2 metals, elements with large ionic potentials which form soluble oxyanions, and group 7 anions
Where is dissolved organic carbon (DOC) usually present
In humic substances
What is the master variable in natural waters?
pH
What is the pH of freshwater
5-11
What is the pH of seawater
around 8
define chemical equilibrium and exceptions
The state of dynamic balance where the rates of opposing reactions are equal and the concentrations remain unchanged. exception: very Slow Reaction such as weathering of aluminium-silicate rock, concentration of species unchanging, non-equilibrium
How are equilibrium reactions quantified
using the equilibrium constant (k) derived from the law of mass action
Give the mass action expression for A + B -> C + D
k = [C] [D] / [A] [B]
Define non-ideal behaviour
Where the concentration of a species is not the same as the actual concentration due to electrostatic interactions between ionic species
Define a homogeneous reaction
where the reaction involves only one phase for example gaseous,
What is the constant concentration of most natural and sea water?
55.5 M dm-3
What 3 things can a mass action expression determine?
whether a system is at equilibrium, which way it will go if not at equilibrium, determines the equilibrium concentration of a species
What effects do temperature and pressure have on k?
significant, pressure only significant for gas phase and in deep waters
6 examples of reactions that can be shown by mass action expressions
Dissociation, acid-base, complexation, redox, gas solution, precipitation-dissolution
Define Henry's law
The mass of gas dissolved by a given volume of liquid at a fixed temperature is proportional to the partial pressure of gas
K for a precipitation-dissolution reaction is called a...
Solubility product Ksp
What happens in the mass action equations when k values are obtained from any set of standard tables?
The effective concentrations of an pure solid or liquid are omitted
What happens when the concentration product is larger than Ksp?
Solution is supersaturated, non-equilibrium
What happens when the concentration product is the same as Ksp?
Solution is saturated, equilibrium
What happens when the concentration product is smaller than Ksp?
Solution is undersaturated, non-equilibrium
Define an acid
An acid is a substance that can donate a proton to any other substance in aqueous solution (i.e. a proton donor
Define a base
A base is a substance that can accept a proton from another substance in aqueous solution (i.e. proton acceptor)
Define amphoteric and example
displays both acid and base properties (HCO3-)
Define polyprotic acids and example
can donate more than one proton e.g. H2SO4
Define polyprotic base and example
can accept more than one proton e.g. OH-
What is K for strong acid and bases
infinite
What is K for weak acid and bases
small (e.g. 10^-6.5)
Give the equation for working out pH from hydrogen ions
pH = -log10 [H+]
The net electric charge of neutral waters is...
0, anions = cations
Write out mass action expression for dissociation of water
k = [H+] [OH-]
Effect of pH on reactions - protons and equilibrium
proton transfer usually very rapid in aqueous solution, equilibrium concepts applicable where dissolved species involved.
2 main sources of CO2 for water
Respiration and the atmosphere
K1 for the dissociation of carbonic acid
k1 = [HCO3-] [H+] / [H2CO3]