I know some people add it direct to the soil, but I reckon its better to put it into compost bin myself as like most things it seems to work better when "matured". Also I have found that neat wood ash is very and can be detrimental to some plant species if its applied direct. Wood ash also helps stop the compost going too acidic.
When wood burns the remaining ash is predominantly pottasium carbonate (potash) and sodium carbonate (soda ash). These act as valuable liming agents, raising pH, thus neutralising acid soils. So soils that are acid and low in potassium will particularly benefit from wood ash. However, acid-loving plants such as azaleas will not appreciate wood ash. The average ash is equivalent to a 0-1-3 (N-P-K).
Potassium is essential to plant growth being an important catalyst in photosynthesis and its essential for seed formation. So I would thoroughly recommend that you add wood ash to your compost heap as part of a healthy balanced diet along with plenty of other compostable materials like leaves, flowers, garden waste, cardboard, shredded paper, tea bags, fruit and vegetable peelings.
I would have to add though that ash from coal fires should never be added to the soil because it will contain traces of potentially harmful substances. Also I would suggest you protect yourself as you would if you were handling household bleach or any other strong alkaline material. Wear eye protection, gloves and a dust mask.
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